CN103314126A - Grain-oriented magnetic steel sheet and process for manufacturing same - Google Patents

Grain-oriented magnetic steel sheet and process for manufacturing same Download PDF

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CN103314126A
CN103314126A CN2012800052397A CN201280005239A CN103314126A CN 103314126 A CN103314126 A CN 103314126A CN 2012800052397 A CN2012800052397 A CN 2012800052397A CN 201280005239 A CN201280005239 A CN 201280005239A CN 103314126 A CN103314126 A CN 103314126A
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quality
temperature
epithelium
annealing
steel
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CN103314126B (en
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高桥史明
牛神义行
水上和实
中村修一
藤井宣宪
山本纪宏
浦乡将英
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Nippon Steel Corp
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
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    • C21D6/00—Heat treatment of ferrous alloys
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Abstract

A grain-oriented magnetic steel sheet which contains 0.8 to 7 mass% of Si, 0.05 to 1 mass% of Mn, and 0.0005 to 0.0080 mass% of B, and has an Al content of 0.025 mass% or less, with the contents of C, N, S and Se being each 0.005 mass% or less, the balance consisting of Fe and unavoidable impurities, and which has a glass film made of a forsterite-based complex oxide on the surface of the steel sheet, characterized in that when a secondary film formed on the surface of the glass film under prescribed conditions is subjected to surface analysis by glow discharge atomic emission spectroscopy (GDS), a peak of emission intensity assignable to B appears at a distance from the peak of emission intensity assignable to Mg, and the position of the peak of emission intensity assignable to B is deeper, beneath the surface of the steel sheet, than the position of the peak of emission intensity assignable to Mg.

Description

Grain-oriented magnetic steel sheet and manufacture method thereof
Technical field
The present invention relates to for the epithelium characteristic that improves grain-oriented magnetic steel sheet and magnetic properties manufacture method.The application here cites its content based on the Japanese Patent Application 2011-4359 number opinion right of priority of on January 12nd, 2011 in Japanese publication.
Background technology
Because grain-oriented magnetic steel sheet mainly uses in the magnetic core of transformer material at electric power, therefore need to hang down iron loss.The manufacture method of grain-oriented magnetic steel sheet is as follows: the cold steel plate that prolongs of making final thickness of slab is implemented decarburizing annealing, then experience take secondary recrystallization and the final annealing that purifies as purpose, then experience forms the operation of epithelium (by overlay film, film) at surface of steel plate.The grain-oriented magnetic steel sheet that carries out in this wise and obtain is by the steel plate that contains Si with sharp-pointed (110) (001) texture (Gauss's orientation) and be formed on its lip-deep several microns inanimate matter epithelium formation.It is that integral condition has been utilized the grain growing that is called as secondary recrystallization that makes Gauss be orientated the particle selection growth in order to realize this tissue in final annealing for the low iron loss characteristic of realizing grain-oriented magnetic steel sheet that steel plate has Gauss's orientation.
In order stably to cause secondary recrystallization, in grain-oriented magnetic steel sheet, utilized the nano-precipitation in the steel that is called as inhibitor.Thereby inhibitor is to be suppressed at low-temp. portion to divide the generation grain growing, decompose or the thick material that makes steel plate forfeiture pinning effect cause secondary recrystallization that becomes by generation more than certain temperature in final annealing, usually utilizes sulfide, nitride.For the organization need that obtains to expect is retained to certain temperature with inhibitor, and if be sulfide, then the sulphur composition dividing potential drop of final annealing is controlled, if nitride is then controlled nitrogen partial pressure, achieve the goal by such grade.For the secondary recrystallization that midway occurs in the intensification in the final annealing, be necessary as sulfide, the nitride of inhibitor, if but they remain in the goods iron loss of goods is significantly worsened.In order from steel plate, to remove the impact of sulfide, nitride, after secondary recrystallization finishes, in pure hydrogen, with about 1200 ℃, keep for a long time.This is called as to purify anneals.Therefore, in purifying annealing, steel plate is for being held state at high temperature in final annealing.
On the other hand, the epithelium of grain-oriented magnetic steel sheet is made of glass epithelium and secondary epithelium, and the tension force that these epitheliums are endowed by steel plate obtains magnetic domain control effect, improves low iron loss characteristic.As described in patent documentation 1 and since mentioned strain when high iron loss to improve effect strong, the ability that therefore produces high tensile especially is required for the secondary epithelium.
Usually the SiO in the steel plate when final annealing 2MgO reaction with as the annealing separation agent main component forms the glass epithelium at steel plate.Have two functions in the glass epithelium.As first function, securely driving fit of glass epithelium and steel plate (adhesion), himself brings tension force to give effect to steel plate, and during the secondary epithelium that after forming final annealing, forms in the operation as guaranteeing that the middle layer with the adaptation of this steel plate works.If the adaptation of glass epithelium is good, then can form the secondary epithelium that produces high tensile, therefore can reach low iron loss by higher magnetic domain control effect.In addition, as second function, the glass epithelium has the function that prevents that the intensity of being brought by inhibitor from excessively reducing, making secondary recrystallization to become stable in final annealing.Therefore, in order stably to make the grain-oriented magnetic steel sheet with good magnetic properties, need to form the glass epithelium good with the adaptation of steel plate.
In grain-oriented magnetic steel sheet, for the adaptation (adhesivity) that improves glass epithelium and steel plate, need to be with the interface structure optimization between glass epithelium and the steel plate.Yet, for existing grain-oriented magnetic steel sheet, when wanting to give situation than in the past high tension force etc., may not necessarily guarantee sufficient adaptation.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 7-207424 communique
Patent documentation 2: TOHKEMY 2003-27196 communique
Patent documentation 3: TOHKEMY 2004-76143 communique
Patent documentation 4: TOHKEMY 2000-204450 communique
Patent documentation 5: Japanese kokai publication hei 6-17261 communique
Patent documentation 6: international disclosing No. 2011/7771
Patent documentation 7: Japanese Patent Publication 60-55570 communique
Patent documentation 8: TOHKEMY 2008-1977 communique
Summary of the invention
Invent problem to be solved
The object of the invention is to, provide and to form the epithelium that produces high tensile, have the glass epithelium of epithelium adaptation excellence and have grain-oriented magnetic steel sheet and the manufacture method thereof of good magnetic properties.
For the means of dealing with problems
Purport of the present invention is as follows.
(1) a kind of grain-oriented magnetic steel sheet, it contains the Mn of Si, the 0.05 quality %～1 quality % of 0.8 quality %～7 quality %, the B of 0.0005 quality %～0.0080 quality %, the containing ratio of Al is below the 0.025 quality %, the content of C, N, S and Se is respectively below the 0.005 quality %, remainder is made of Fe and inevitable impurity, have on the surface of steel plate by with forsterite as the glass epithelium that the composite oxides of main body form, it is characterized in that
Formed thickness on the surface of described glass epithelium and be more than the 1 μ m and when under the condition of the secondary epithelium below the 2 μ m surface of described secondary epithelium being carried out grow discharge optical emission spectrometry analysis (GDS), peak with luminous intensity of the peak position of the luminous intensity B different from the peak position of the luminous intensity of Mg, the peak position of the luminous intensity of the B of the described surface of steel plate of distance is darker than the peak position of the luminous intensity of the Mg of the described surface of steel plate of distance, wherein, described secondary epithelium forms by following step: coating contains in chromic trioxide and the chromic salt a kind or 2 kinds of being selected from of the colloidal silicon-dioxide of 26～38 % by weight and 4～12 quality %, and coating liquid and drying that remainder is made of aluminium dihydrogen phosphate, then 800 ℃～900 ℃ lower bakings
And among the peak of the luminous intensity of the described B that observes by grow discharge optical emission spectrometry analysis (GDS), apart from described surface of steel plate farthest person's peak generation time tB represent with following formula (1).
tMg×1.6≤tB≤tMg×5?（1）
Herein, tMg represents the peak generation time of Mg.
(2) a kind of manufacture method of grain-oriented magnetic steel sheet is characterized in that, it has following operation:
Heating process, in this operation, the electro-magnetic steel plate starting material are heated under the temperature of regulation, described electro-magnetic steel plate starting material contain Si, the 0.01 quality % of 0.8 quality %～7 quality %～acid-solubility Al of 0.065 quality %, the Mn of the N of 0.004 quality %～0.012 quality %, 0.05 quality %～1 quality %, the B of 0.0005 quality %～0.0080 quality %, and among S and the Se at least a kind of being selected from that contains 0.003 quality %～0.015 quality % by total amount, C content is below the 0.085 quality %, and remainder is made of Fe and inevitable impurity;
Obtain the operation of hot rolled strip, in this operation, warmed-up described silicon steel starting material are carried out hot rolling obtain hot rolled strip;
Obtain the annealing operation of steel band in this operation, anneals to obtain the steel band of annealing to described hot rolled strip;
Obtain the operation of cold-rolled steel strip, in this operation, described annealed steel band is carried out the cold rolling cold-rolled steel strip that obtains more than 1 time;
Obtain the operation of decarburizing annealing steel band, in this operation, described cold-rolled steel strip is carried out decarburizing annealing, thereby obtained occuring the decarburizing annealing steel band of primary recrystallization;
Painting process in this operation, will be coated described decarburizing annealing steel band as the annealing separation agent of main component with MgO; With
The operation of secondary recrystallization occurs, and in this operation, makes the operation of its generation secondary recrystallization by the final annealing of described decarburizing annealing steel band,
And the manufacture method of described grain-oriented magnetic steel sheet also has following operation: from begin described decarburizing annealing manifest to the final annealing secondary recrystallization during, the nitriding treatment that the N content of described decarburizing annealing steel band is increased,
When containing S and Se in the described silicon steel starting material, the temperature of described regulation is temperature T 1(℃ shown in the following formula (2)) temperature T 2(℃ shown in following, the following formula (3)) temperature T 3(℃ shown in the following and following formula (4)) below; When not containing Se in the described silicon steel starting material, the temperature of described regulation is temperature T 1(℃ shown in the following formula (2)) temperature T 3(℃ shown in the following and following formula (4)) below; When not containing S in the described silicon steel starting material, the temperature of described regulation is temperature T 2(℃ shown in the following formula (3)) temperature T 3(℃ shown in the following and following formula (4)) below, the finish rolling end temp Tf of described hot rolling satisfies following formula (5), the amount of BN in the described hot rolled strip, MnS and MnSe satisfies following formula (6), (7) and (8), and the temperature during final annealing is 800 ℃～1100 ℃ temperature range, and atmosphere satisfies following formula (9) and (10).
T1=14855/(6.82-log([Mn]×[S]))-273?（2）
T2=10733/(4.08-log([Mn]×[Se]))-273?（3）
T3=16000/(5.92-log([B]×[N]))-273?（4）
Tf≤1000-10000×[B]?（5）
B asBN≥0.0005?（6）
[B]-B asBN≤0.001?（7）
S asMnS+0.5×Se asMnSe≥0.002?（8）
0.75≥P N2≥0.2?（9）
-0.7≥Log[P H2O/P H2]?（10）
Herein, [Mn] represents the raw-material Mn content of described silicon steel (quality %), [S] represents the raw-material S content of described silicon steel (quality %), [Se] represents the raw-material Se content of described silicon steel (quality %), [B] represents the raw-material B content of described silicon steel (quality %), [N] represents the raw-material N content of described silicon steel (quality %), B AsBNBe illustrated in the amount (quality %) of the B that separates out as BN in the described hot rolled strip, S AsMnSBe illustrated in the amount (quality %) of the S that separates out as MnS in the described hot rolled strip, Se AsMnSeBe illustrated in the amount (quality %) of the Se that separates out as MnSe in the described hot rolled strip.And, P N2The expression nitrogen partial pressure, P H2O, P H2Represent respectively steam partial pressure, hydrogen dividing potential drop.
(3) according to the manufacture method of the described grain-oriented magnetic steel sheet of preceding paragraph (2), it is characterized in that, the temperature during final annealing is 800 ℃～1100 ℃ temperature range, and the atmosphere during final annealing satisfies formula (11).
4Log[P N2]=3Log[P H2O/P H2]+A+3455/T?（11）
Herein ,-3.72 〉=3Log[P H2O/ P H2]+A 〉=-5.32 and-0.7 〉=Log[P H2O/ P H2], A is for pressing based on Log[P H2O/ P H2] make 3Log[P H2O/ P H2]+A enters the definite constant of mode of the scope of regulation, and T represents absolute temperature.
(4) according to the manufacture method of the described grain-oriented magnetic steel sheet of preceding paragraph (2), it is characterized in that, the atmosphere when final annealing more than 1100 ℃ satisfies formula (12) and (13).
0.1≥P N2?（12）
-2≥Log[P H2O/P H2]?（13）
(5) according to the manufacture method of the described grain-oriented magnetic steel sheet of preceding paragraph (2), it is characterized in that, described electro-magnetic steel plate starting material further contain be selected from that Cr:0.3 quality % is following, Cu:0.4 quality % following, Ni:1 quality % is following, P:0.5 quality % is following, Mo:0.1 quality % is following, Sn:0.3 quality % is following, Sb:0.3 quality % is following and Bi:0.01 quality % with lower at least a kind.
The invention effect
According to the present invention, can access and to form the epithelium that produces high tensile, have the glass epithelium of epithelium adaptation excellence and the grain-oriented magnetic steel sheet with good magnetic properties.
Description of drawings
Fig. 1 is grow discharge optical emission spectrometry analysis (GDS) result's on expression grain-oriented magnetic steel sheet surface the figure of schematic diagram.
Fig. 2 be expression in the hot rolled strip the precipitate amount and the figure of the relation between the magnetic properties behind the final annealing.
Fig. 3 be expression in the hot rolled strip the precipitate amount and the figure of the relation between the epithelium adaptation behind the final annealing.
Fig. 4 represents not the amount of the B that separates out as BN and the figure of the relation between the magnetic properties behind the final annealing.
Fig. 5 represents not the amount of the B that separates out as BN and the figure of the relation between the epithelium adaptation behind the final annealing.
Fig. 6 is the condition of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Fig. 7 is the condition of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Fig. 8 is the condition of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Fig. 9 is the condition of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 10 is the finish rolling end temp of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Figure 11 is the finish rolling end temp of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 12 is the precipitate of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Figure 13 is the precipitate of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 14 represents not the amount of the B that separates out as BN and the figure of the relation between the magnetic properties behind the final annealing.
Figure 15 represents not the amount of the B that separates out as BN and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 16 is the condition of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Figure 17 is the condition of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Figure 18 is the condition of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 19 is the condition of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 20 is the finish rolling end temp of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Figure 21 is the finish rolling end temp of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 22 be expression in the hot rolled strip the precipitate amount and the figure of the relation between the magnetic properties behind the final annealing.
Figure 23 be expression in the hot rolled strip the precipitate amount and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 24 represents not the amount of the B that separates out as BN and the figure of the relation between the magnetic properties behind the final annealing.
Figure 25 represents not the amount of the B that separates out as BN and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 26 is the condition of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Figure 27 is the condition of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Figure 28 is the condition of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 29 is the condition of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 30 is the finish rolling end temp of expression hot rolling and the figure of the relation between the magnetic properties behind the final annealing.
Figure 31 is the finish rolling end temp of expression hot rolling and the figure of the relation between the epithelium adaptation behind the final annealing.
Figure 32 is the ratio tB/tMg of expression GDS analytical results and the figure of the relation between the epithelium adaptation.
Embodiment
In the past, B utilized as the additive of the annealing separation agent of grain-oriented magnetic steel sheet, and inventors find that in the situation that B is added in the steel plate, the epithelium adaptation is improved with magnetic properties sometimes.Therefore, the sample that shows superperformance is studied in great detail.Found that the distribution that is characterised in that the at the interface B between glass epithelium and steel plate.That is, find by the interface structure optimization between glass epithelium and the steel plate can be improved magnetic properties and epithelium adaptation.Above-mentioned interface structure possesses following feature.Namely, at Mn, the 0.0005 quality %～B of 0.0080 quality %, the containing ratio of Al of the Si that contains 0.8 quality %～7 quality % as steel plate integral body, 0.05 quality %～1 quality % be below the 0.025 quality %, the content of C, N, S and Se is respectively below the 0.005 quality % and remainder by Fe with in the grain-oriented magnetic steel sheet that inevitably impurity consists of, surface of steel plate have by with forsterite as the composite oxides of main body forms layer.
The meaning of forsterite as main body referred to herein, for the constituent of epithelium, forsterite accounts for more than 70 % by weight as the formation compound of epithelium.And, be characterised in that: in the situation that surface of steel plate is carried out grow discharge optical emission spectrometry analysis (GDS), the peak that has the luminous intensity of B in the position different from the peak position of Mg, its position apart from surface of steel plate is darker than Mg.Particularly, be characterised in that: as shown in Figure 1, in the peak of the B that observes by GDS, be the distance more than necessarily apart from the position at the peak of Mg apart from the distance on surface of steel plate peak farthest and surface.
The sample of making by various conditions in the 1st following test is studied, analyzed the peak of this Mg and the relation between the adaptation, the result obtains the result shown in Figure 32.Peak position with Mg is made as tMg herein, is positioned in the peak with B apart from the position at the peak of the surperficial deepest part of steel plate to be made as tB.In addition, in Figure 32, the result who obtains with the ratio tB/tMg arrangement of tMg, tB value is shown for magnetic properties.In addition, peeling off the fewer demonstration adaptation of area in Figure 32 more improves.
Shown in figure 32, tB 〉=tMg * 1.6 o'clock as can be known, the area of peeling off of epithelium is below 5%, and it is slight peeling off, and adaptation improves.On the other hand, magnetic properties also is that the tB value can improve when large, but the tB value is sometimes deteriorated on the contrary when excessive, so ratio tB/tMg is made as below 5.
In addition, in the situation that measure tB, tMg value by GDS, the thickness of the secondary epithelium on the glass epithelium is made as rigid condition measures.For example, be more than the 1 μ m and in the situation of the secondary epithelium below the 2 μ m having formed thickness, can directly measure by GDS, above-mentioned secondary epithelium forms by following step: what coating contained the colloidal silicon-dioxide of 26～38 % by weight and 4～12 quality % is selected from coating liquid that in chromic trioxide and the chromic salt a kind or 2 kinds and remainder be made of aluminium dihydrogen phosphate and dry, then 800 ℃～900 ℃ lower bakings.Yet, composition at the secondary epithelium, in the situation that thickness is failed to understand, removing the secondary epithelium with aqueous sodium hydroxide solution etc. and after the surface of glass epithelium is exposed, as mentioned above, be more than the 1 μ m and under the state of the secondary epithelium below the 2 μ m having formed thickness, measure tB by GDS, the tMg value, above-mentioned secondary epithelium forms by following step: coating contains in chromic trioxide and the chromic salt a kind or 2 kinds of being selected from of the colloidal silicon-dioxide of 26～38 % by weight and 4～12 quality %, and coating liquid and drying that remainder is made of aluminium dihydrogen phosphate are then 800 ℃～900 ℃ lower bakings.By forming the secondary epithelium of such compositing range and thickness range, can be with enough precision determination tB, tMg value.
Be as can be known electro-magnetic steel plate with following characteristics by this result: analyze in the situation that carried out GDS by glass epithelium surface, respectively with the peak position in the deep of the enrichment of B to represent discharge time and be made as tB(second), the peak position of Mg is made as tMg(second) time, the peak position of Mg represents with (1) formula.
tMg×1.6≤tB≤tMg×5?（1）
Mg is almost all from the glass epithelium.Therefore, in the situation that the secondary epithelium is thicker, the peak position of Mg changes, and the peak position of B changes.In order to avoid this impact, stipulated in the present invention the thickness of the secondary epithelium when GDS measures.In addition, if contain in a large number Mg in the secondary epithelium of sheet, then the peak from the Mg of glass epithelium becomes indefinite.Consider from above-mentioned situation, in order to estimate (1) formula, need to use and removed the value of measuring behind this secondary epithelium.In addition, the regulation of the thickness of secondary epithelium, composition and formation condition is to carry out the Pretreatment of GDS when measuring, and is not the state of the secondary epithelium etc. of regulation sheet.
For the structure that realizes being determined by (1) formula, by as described (3) middle put down in writing such, regulation take Si as representative composition and these electro-magnetic steel plate starting material are processed with the temperature of regulation, perhaps get final product by described (4) and (5) middle method of putting down in writing.
The＜the 1 test＞
Below, the content of the test that reaches above such opinion is described.At first, for the relation between precipitate and magnetic properties and the epithelium adaptation, carry out the test that the silicon steel starting material with the composition that contains S are studied.
At first, obtain following various blank plates of silicon steels: it contains Si:3.3 quality %, C:0.06 quality %, acid-solubility Al:0.027 quality %, N:0.008 quality %, Mn:0.05 quality %～0.19 quality %, S:0.007 quality % and B:0.0010 quality %～0.0035 quality %, and remainder is made of Fe and inevitable impurity.Then, under 1100 ℃～1250 ℃ temperature, heat blank plates of silicon steels, carry out hot rolling.Hot rolling is carried out roughing exactly under 1050 ℃, then carry out finish rolling under 1000 ℃, obtains the hot rolled strip that thickness is 2.3mm.Then, hot rolled strip shower cooling water is cooled to 550 ℃, then in atmosphere, cools off.Next, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, the speed heats cold strip rolling with 15 ℃/second carries out decarburizing annealing under 840 ℃ temperature, thereby obtains the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.022 quality %.Then, coating is carried out final annealing with the annealing separation agent of MgO as main component.About the atmosphere of final annealing, with the nitrogen partial pressure P of 800 ℃～1100 ℃ atmosphere N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1.0, with the nitrogen partial pressure P of the atmosphere more than 1100 ℃ N2Be made as below 0.1, with oxygen gesture Log[P H2O/ P H2] be made as-below 2, make various samples.
Next, precipitate in the hot rolled strip and relation between the magnetic properties behind the final annealing have been studied.This results are shown in Fig. 2.Ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.X-coordinate is equivalent to the amount (quality %) of the S that separates out as MnS.In addition, white circle expression magneticflux-density B8 is more than the 1.88T, and black square represents that magneticflux-density B8 is less than 1.88T.As shown in Figure 2, in the sample of the amount of separating out less than certain value of MnS or BN, magneticflux-density B8 is low.This situation represents that secondary recrystallization is unstable.
On the other hand, analyzed relation between the situation of precipitate and the epithelium adaptation behind the final annealing.For clear and definite adaptation improves effect, to estimate than the more secondary epithelium of the amount of common weight per unit area amount.If make the amount of weight per unit area of secondary epithelium many, then becoming when the adaptation that steel plate is applied high tensile, glass epithelium is insufficient easily produces epithelium and peels off.For this test, at first as the secondary epithelium, making by solid component concentration is that 50% aluminum phosphate 100g, solid component concentration are 20% colloid silica 102g, the coating fluid that chromic trioxide 5.4g forms.Next, to the steel plate with glass epithelium behind the final annealing by becoming single face 10g/m 2Mode be coated with this coating fluid, after the drying, 900 ℃ of lower bakings.After this steel plate was wound to the pole of 20 φ, the area of peeling off that exposes such epithelium at the inboard steel plate of curved part was 5% when following, is judged as adaptation good.This results are shown in Fig. 3.In Fig. 3, white circle expression adaptation is good, and black square represents to exist that epithelium is peeled off, adaptation and in the past be equal extent.As shown in Figure 3, in the amount of separating out of MnS and BN is sample more than the certain value, confirm the raising of epithelium adaptation.
In addition, to having separated out a certain amount of above MnS and the sample of BN, the amount of the B that separates out as BN and the relation between the magnetic properties behind the final annealing have been studied not.This results are shown in Fig. 4.The X-coordinate of Fig. 4 represents B content (quality %), and ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.In addition, white circle expression magneticflux-density B8 is more than the 1.88T, and black square represents that magneticflux-density B8 is less than 1.88T.As shown in Figure 4, in the amount of the B that does not separate out as BN was sample more than the certain value, magneticflux-density B8 was low.This situation represents that secondary recrystallization is unstable.
Similarly, to having separated out a certain amount of above MnS and the sample of BN, the amount of the B that separates out as BN and the relation between the epithelium adaptation behind the final annealing have been studied not.This results are shown in Fig. 5.About the evaluation of adaptation, undertaken by the method identical with the method for in the explanation of Fig. 3, narrating.As shown in Figure 5, in the amount of separating out of BN is sample more than the certain value, confirm the raising of epithelium adaptation.
In addition, to magnetic properties and the good sample of epithelium adaptation, studied the form of precipitate, the result distinguishes that BN is take MnS as compound the separating out around MnS of nuclear.Such miscible precipitate is effective as the inhibitor that makes secondary recrystallization become stable.In addition, become appropriately by the atmosphere that makes final annealing, BN is decomposed in appropriate temperature province and B is supplied to during formation at the glass epithelium interface of steel plate and glass epithelium, finally help the raising of epithelium adaptation.
In addition, the condition of hot rolling and the relation between the magnetic properties behind the final annealing have been studied.This results are shown in Fig. 6 and Fig. 7.
The X-coordinate of Fig. 6 represents Mn content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).The X-coordinate of Fig. 7 represents B content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).In addition, white circle expression magneticflux-density B8 is more than the 1.88T, and black square represents that magneticflux-density B8 is less than 1.88T.In addition, the solid solubility temperature T1(of the MnS shown in the following formula of the curve representation among Fig. 6 (2) ℃), the solid solubility temperature T3(of the BN shown in the following formula of the curve representation among Fig. 7 (4) ℃).As shown in Figure 6, distinguish below with definite temperature corresponding to Mn content and carried out in the sample of heating of plate blank, obtain high magneticflux-density B8.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T1 of MnS.In addition, as shown in Figure 7, also distinguish below with definite temperature corresponding to B content and carried out in the sample of heating of plate blank, obtain high magneticflux-density B8.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T3 of BN.That is, distinguish that it is effective not carrying out heating of plate blank in the temperature province of solid solution fully at MnS and BN.
T1=14855/(6.82-log([Mn]×[S]))-273?（2）
T3=16000/(5.92-log([B]×[N]))-273?（4）
Herein, [Mn] represents Mn content (quality %), and [S] represents S content (quality %), and [B] represents B content (quality %), and [N] represents N content (quality %).
And then, the Precipitation Characteristics of BN is studied, the result distinguishes that its Precipitation Temperature zone is 800 ℃～1000 ℃.
Similarly, studied relation between the condition of hot rolling and the epithelium adaptation behind the final annealing.About the evaluation of adaptation, undertaken by the method identical with the method for in the explanation of Fig. 3, narrating.This results are shown in Fig. 8 and Fig. 9.The X-coordinate of Fig. 8 represents Mn content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).In addition, white circle expression epithelium adaptation is no problem, and black square represents to exist epithelium to peel off.In addition, solid solubility temperature T1(℃ of the MnS shown in the curve representation formula (2) among Fig. 8), solid solubility temperature T3(℃ of the BN shown in the curve representation formula (4) among Fig. 9).As shown in Figure 8, distinguish below with definite temperature corresponding to Mn content and carried out in the sample of heating of plate blank, obtain the epithelium adaptation and improve effect.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T1 of MnS.In addition, as shown in Figure 9, also distinguish below with definite temperature corresponding to B content and carried out in the sample of heating of plate blank, obtain the epithelium adaptation and improve effect.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T3 of BN.
In addition, inventors of the present invention are studied the finish rolling end temp of hot rolling.In this research, at first, obtain following various blank plates of silicon steels: it contains Si:3.3 quality %, C:0.06 quality %, acid-solubility Al:0.027 quality %, N:0.008 quality %, Mn:0.1 quality %, S:0.007 quality % and B:0.001 quality %～0.004 quality %, and remainder is made of Fe and inevitable impurity.Then, blank plates of silicon steels is heated under 1200 ℃ temperature, carry out hot rolling.Hot rolling is carried out roughing exactly under 1050 ℃, then carry out finish rolling under 1020 ℃～900 ℃, obtains the hot rolled strip that thickness is 2.3mm.Then, hot rolled strip shower cooling water is cooled to 550 ℃, then in atmosphere, cools off.Next, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, the speed heats cold strip rolling with 15 ℃/second carries out decarburizing annealing under 840 ℃ temperature, thereby obtains the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.022 quality %.Then, coating is carried out final annealing with the annealing separation agent of MgO as main component.About the atmosphere of final annealing, with the nitrogen partial pressure P of 800 ℃～1100 ℃ atmosphere N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1.0, with the nitrogen partial pressure P of the atmosphere more than 1100 ℃ N2Be made as below 0.1, with oxygen gesture Log[P H2O/ P H2] be made as-below 2, make various samples.
Then, the finish rolling end temp of hot rolling and the relation between the magnetic properties behind the final annealing have been studied.This results are shown in Figure 10.The X-coordinate of Figure 10 represents B content (quality %), and ordinate zou represents finish rolling end temp Tf.In addition, white circle expression magneticflux-density B8 is more than the 1.91T, and black square represents that magneticflux-density B8 is less than 1.91T.As shown in figure 10, distinguish in the situation that finish rolling end temp Tf satisfies following formula (5), obtain high magneticflux-density B8.This can think that separating out further of BN is promoted owing to the control by finish rolling end temp Tf.
Tf≤1000-10000×[B]?（5）
In addition, the finish rolling end temp of hot rolling and the relation between the epithelium adaptation behind the final annealing have been studied.About the evaluation of adaptation, undertaken by the method identical with the method for in the explanation of Fig. 3, narrating.This results are shown in Figure 11.The X-coordinate of Figure 11 represents B content (quality %), and ordinate zou represents finish rolling end temp Tf.In addition, white circle expression epithelium adaptation is good, and black square represents to exist epithelium to peel off.As shown in figure 11, distinguish by making finish rolling end temp Tf satisfy formula (5) and the atmosphere of final annealing being become appropriately, can obtain the effect of improving of epithelium adaptation.
The＜the 2 test＞
Then, for the relation between precipitate and magnetic properties and the epithelium adaptation, carry out the test that the silicon steel starting material with the composition that contains Se are studied.
At first, obtain various blank plates of silicon steels: it contains Si:3.3 quality %, C:0.06 quality %, acid-solubility Al:0.028 quality %, N:0.007 quality %, Mn:0.05 quality %～0.20 quality %, Se:0.007 quality % and B:0.0010 quality %～0.0035 quality %, and remainder is made of Fe and inevitable impurity.Then, under 1100 ℃～1250 ℃ temperature, heat blank plates of silicon steels, carry out hot rolling.Hot rolling is carried out roughing exactly under 1050 ℃, then carry out finish rolling under 1000 ℃, obtains the hot rolled strip that thickness is 2.3mm.Then, hot rolled strip shower cooling water is cooled to 550 ℃, then in atmosphere, cools off.Next, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, the speed heats cold strip rolling with 15 ℃/second carries out decarburizing annealing under 850 ℃ temperature, thereby obtains the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.023 quality %.Then, coating is with the annealing separation agent of MgO as main component, with the nitrogen partial pressure P of 800 ℃～1100 ℃ atmosphere N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1.0, with the nitrogen partial pressure P of the atmosphere more than 1100 ℃ N2Be made as below 0.1, with oxygen gesture Log[P H2O/ P H2] be made as-2 and carry out final annealing to get off, make various samples.
Then, precipitate in the hot rolled strip and relation between the magnetic properties behind the final annealing have been studied.This results are shown in Figure 12.The X-coordinate of Figure 12 represents that the amount of separating out with MnSe is converted into the amount of Se and the value (quality %) that obtains, and ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.In addition, white circle expression magneticflux-density B8 is more than the 1.88T, and black square represents that magneticflux-density B8 is less than 1.88T.As shown in figure 12, in the sample of the amount of separating out less than certain value of MnSe or BN, magneticflux-density B8 is low.This situation represents that secondary recrystallization is unstable.
Similarly, precipitate in the hot rolled strip and relation between the epithelium adaptation behind the final annealing have been studied.About the evaluation of epithelium adaptation, similarly carry out with the method for in the explanation of Fig. 3, narrating.This results are shown in Figure 13.The X-coordinate of Figure 13 represents that the amount of separating out with MnSe is converted into the amount of Se and the value (quality %) that obtains, and ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.In addition, white circle expression epithelium adaptation is good, and black square represents to have produced epithelium and peels off.As shown in figure 13, be the situation of appropriate condition in the atmosphere of final annealing in the amount of separating out of MnSe and BN in for the sample more than certain as can be known, have the effect of improving of epithelium adaptation.
In addition, to having separated out a certain amount of above MnSe and the sample of BN, the amount of the B that separates out as BN and the relation between the magnetic properties behind the final annealing have been studied not.This results are shown in Figure 14.The X-coordinate of Figure 14 represents B content (quality %), and ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.In addition, white circle expression magneticflux-density B8 is more than the 1.88T, and black square represents that magneticflux-density B8 is less than 1.88T.As shown in figure 14, in the amount of the B that does not separate out as BN was sample more than the certain value, magneticflux-density B8 was low.This situation represents that secondary recrystallization is unstable.
Similarly, to having separated out a certain amount of above MnSe and the sample of BN, the amount of the B that separates out as BN and the relation between the epithelium adaptation behind the final annealing have been studied not.About the evaluation of epithelium adaptation, identical with the method for in the explanation of Fig. 3, narrating.This results are shown in Figure 15.The X-coordinate of Figure 15 represents B content (quality %), and ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.In addition, white circle is illustrated in to have seen on the epithelium adaptation and improves effect, and black square represents to exist epithelium to peel off, and is not improving effect aspect the epithelium adaptation.As shown in figure 15, be in the situation of the appropriate condition of the atmosphere of sample below the certain value and final annealing in the amount for the B that do not separate out as BN, see the effect of improving of epithelium adaptation.
In addition, to magnetic properties, the good sample of epithelium adaptation, studied the form of precipitate, the result distinguishes that BN is take MnSe as compound the separating out around MnSe of nuclear.Such miscible precipitate is effective as the inhibitor that makes secondary recrystallization become stable.In addition, in the appropriate situation of the atmosphere of final annealing, BN is decomposed in appropriate temperature province and B is supplied to during formation at the glass epithelium interface of steel plate and glass epithelium, finally help the raising of epithelium adaptation.
In addition, the condition of hot rolling and the relation between the magnetic properties behind the final annealing have been studied.This results are shown in Figure 16 and Figure 17.
The X-coordinate of Figure 16 represents Mn content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).The X-coordinate of Figure 17 represents B content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).In addition, white circle expression magneticflux-density B8 is more than the 1.88T, and black square represents that magneticflux-density B8 is less than 1.88T.In addition, the solid solubility temperature T2(of the MnSe shown in the following formula of the curve representation among Figure 16 (3) ℃), solid solubility temperature T3(℃ of the BN shown in the curve representation formula (4) among Figure 17).As shown in figure 16, distinguish below with definite temperature corresponding to Mn content and carried out in the sample of heating of plate blank, obtain high magneticflux-density B8.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T2 of MnSe.In addition, as shown in figure 17, also distinguish below with definite temperature corresponding to B content and carried out in the sample of heating of plate blank, obtain high magneticflux-density B8.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T3 of BN.That is, distinguish that it is effective not carrying out heating of plate blank in the temperature province of solid solution fully at MnSe and BN.
T2=10733/(4.08-log([Mn]×[Se]))-273?（3）
Herein, [Se] expression Se content (quality %).
Similarly, studied relation between the condition of hot rolling and the epithelium adaptation behind the final annealing.This results are shown in Figure 18 and Figure 19.About the evaluation of epithelium adaptation, identical with the method for in the explanation of Fig. 3, narrating.
The X-coordinate of Figure 18 represents Mn content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).The X-coordinate of Figure 19 represents B content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).In addition, white circle expression epithelium adaptation improves, and black square represents to have epithelium to peel off, and adaptation does not improve.In addition, solid solubility temperature T2(℃ of the MnSe shown in the curve representation formula (3) among Figure 18), solid solubility temperature T3(℃ of the BN shown in the curve representation formula (4) among Figure 19).As shown in figure 18, distinguish below with definite temperature corresponding to Mn content and carried out in the sample of heating of plate blank, the epithelium adaptation improves.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T2 of MnSe.In addition, as shown in figure 19, distinguish below with definite temperature corresponding to B content and carried out in the sample of heating of plate blank to have the epithelium adaptation and improve effect.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T3 of BN.That is, distinguish that it is effective fully not carrying out heating of plate blank, carry out final annealing under appropriate atmosphere in the temperature province of solid solution at MnSe and BN.
And then, the Precipitation Characteristics of BN is studied, the result distinguishes that its Precipitation Temperature zone is 800 ℃～1000 ℃.
In addition, inventors of the present invention are studied the finish rolling end temp of hot rolling.In this research, at first, obtain following various blank plates of silicon steels: it contains Si:3.3 quality %, C:0.06 quality %, acid-solubility Al:0.028 quality %, N:0.007 quality %, Mn:0.1 quality %, Se:0.007 quality % and B:0.001 quality %～0.004 quality %, and remainder is made of Fe and inevitable impurity.Then, blank plates of silicon steels is heated under 1200 ℃ temperature, carry out hot rolling.Hot rolling is carried out roughing exactly under 1050 ℃, then carry out finish rolling under 1020 ℃～900 ℃, obtains the hot rolled strip that thickness is 2.3mm.Next, hot rolled strip shower cooling water is cooled to 550 ℃, then in atmosphere, cools off.Next, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, the speed heats cold strip rolling with 15 ℃/second carries out decarburizing annealing under 850 ℃ temperature, thereby obtains the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.023 quality %.Then, coating is with the annealing separation agent of MgO as main component, with the nitrogen partial pressure P of 800 ℃～1100 ℃ atmosphere N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1, with the nitrogen partial pressure P of the atmosphere more than 1100 ℃ N2Be made as below 0.1, with oxygen gesture Log[P H2O/ P H2] be made as-2, carry out final annealing, make various samples.
Next, the finish rolling end temp of hot rolling and the relation between the magnetic properties behind the final annealing have been studied.This results are shown in Figure 20.The X-coordinate of Figure 20 represents B content (quality %), and ordinate zou represents finish rolling end temp Tf.In addition, white circle expression magneticflux-density B8 is more than the 1.91T, and black square represents that magneticflux-density B8 is less than 1.91T.As shown in figure 20, distinguish in the situation that finish rolling end temp Tf satisfies described formula (13), obtain high magneticflux-density B8.This thinks that separating out further of BN is promoted owing to the control by finish rolling end temp Tf.
Similarly, the finish rolling end temp of hot rolling and the relation between the epithelium adaptation behind the final annealing have been studied.This results are shown in Figure 21.The X-coordinate of Figure 21 represents B content (quality %), and ordinate zou represents finish rolling end temp Tf.In addition, white circle expression epithelium adaptation improves, and black square represents not have epithelium to peel off adaptation raising effect.As shown in figure 21, distinguish at finish rolling end temp Tf and satisfy formula (13) and carrying out under the appropriate atmosphere in the final annealing situation to have the epithelium adaptation and improve effect.
The＜the 3 test＞
Further for the relation between precipitate and magnetic properties and the epithelium adaptation, carry out the test that the silicon steel starting material with the composition that contains S and Se are studied.
At first, obtain following various blank plates of silicon steels: it contains Si:3.3 quality %, C:0.06 quality %, acid-solubility Al:0.026 quality %, N:0.009 quality %, Mn:0.05 quality %～0.20 quality %, S:0.005 quality %, Se:0.007 quality % and B:0.0010 quality %～0.0035 quality %, and remainder is made of Fe and inevitable impurity.Then, under 1100 ℃～1250 ℃ temperature, heat blank plates of silicon steels, carry out hot rolling.Hot rolling is carried out roughing exactly under 1050 ℃, then carry out finish rolling under 1000 ℃, obtains the hot rolled strip that thickness is 2.3mm.Next, hot rolled strip shower cooling water is cooled to 550 ℃, then in atmosphere, cools off.Next, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, the speed heats cold strip rolling with 15 ℃/second carries out decarburizing annealing under 850 ℃ temperature, thereby obtains the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.021 quality %.Then, coating is with the annealing separation agent of MgO as main component, with the nitrogen partial pressure P of 800 ℃～1100 ℃ atmosphere N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1, with the nitrogen partial pressure P of the atmosphere more than 1100 ℃ N2Be made as below 0.1, with oxygen gesture Log[P H2O/ P H2] be made as-below 2, carry out final annealing, make various samples.
Next, precipitate in the hot rolled strip and relation between the magnetic properties behind the final annealing have been studied.This results are shown in Figure 22.The X-coordinate of Figure 22 represents that the amount of separating out with MnS is converted into the amount of S and the value that obtains is converted into the amount of Se with the amount of separating out with MnSe and the value sum (quality %) that obtains with 0.5 on duty that obtains, and ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.In addition, white circle expression magneticflux-density B8 is more than the 1.88T, and black square represents that magneticflux-density B8 is less than 1.88T.As shown in figure 22, in the sample of the amount of separating out less than certain value of MnS and MnSe or BN, magneticflux-density B8 is low.This situation represents that secondary recrystallization is unstable.
Similarly, precipitate in the hot rolled strip and relation between the epithelium adaptation behind the final annealing have been studied.About the evaluation of epithelium adaptation, identical with the method for in the explanation of Fig. 3, narrating.This results are shown in Figure 23.The X-coordinate of Figure 23 represents that the amount of separating out with MnS is converted into the amount of S and the value that obtains is converted into the amount of Se with the amount of separating out with MnSe and the value sum (quality %) that obtains with 0.5 on duty that obtains, and ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.In addition, white circle expression epithelium adaptation improves, and black square represents to have epithelium to peel off and do not have the epithelium adaptation to improve effect.As shown in figure 23, be more than the certain value and the atmosphere of final annealing is that the epithelium adaptation improves in the situation of appropriate condition in the amount of separating out of MnS, MnSe and BN.
In addition, to having separated out a certain amount of above MnS, MnSe and the sample of BN, the amount of the B that separates out as BN and the relation between the magnetic properties behind the final annealing have been studied not.This results are shown in Figure 24.The X-coordinate of Figure 24 represents B content (quality %), and ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.In addition, white circle expression magneticflux-density B8 is more than the 1.88T, and black square represents that magneticflux-density B8 is less than 1.88T.As shown in figure 24, in the amount of the B that does not separate out as BN was sample more than the certain value, magneticflux-density B8 was low.This situation represents that secondary recrystallization is unstable.
Similarly, to having separated out a certain amount of above MnS, MnSe and the sample of BN, the amount of the B that separates out as BN and the relation between the epithelium adaptation behind the final annealing have been studied not.The evaluation method of epithelium adaptation is identical with the method for using in Fig. 3.This results are shown in Figure 25.The X-coordinate of Figure 25 represents B content (quality %), and ordinate zou represents that the amount of separating out with BN is converted into B and the value (quality %) that obtains.In addition, white circle expression epithelium adaptation improves, and black square represents to exist epithelium to peel off, and the epithelium adaptation does not improve.As shown in figure 25, be that the epithelium adaptation improves in the appropriate situation of the atmosphere of sample below the certain value and final annealing in the amount for the B that do not separate out as BN.
In addition, to magnetic properties and the good sample of epithelium adaptation, studied the form of precipitate, the result distinguishes that BN is take MnS or MnSe as compound the separating out around MnS or MnSe of nuclear.Such miscible precipitate is effective as the inhibitor that makes secondary recrystallization become stable.In addition, be made as in the atmosphere with final annealing in the situation of appropriate condition, BN is decomposed in optimal temperature province and when the glass epithelium forms, B is supplied to the interface of steel plate and glass epithelium, finally help the raising of epithelium adaptation.
Then, the condition of hot rolling and the relation between the magnetic properties behind the final annealing have been studied.This results are shown in Figure 26 and Figure 27.
The X-coordinate of Figure 26 represents Mn content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).The X-coordinate of Figure 27 represents B content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).In addition, white circle expression magneticflux-density B8 is more than the 1.88T, and black square represents that magneticflux-density B8 is less than 1.88T.In addition, solid solubility temperature T1(℃ of the MnS shown in two the curve representation formulas (2) among Figure 26) and solid solubility temperature T2(℃ of the MnSe shown in the formula (3)), solid solubility temperature T3(℃ of the BN shown in the curve representation formula (4) among Figure 27).As shown in figure 26, distinguish below with definite temperature corresponding to Mn content and carried out in the sample of heating of plate blank, obtain high magneticflux-density B8.In addition, distinguish that also the solid solubility temperature T2 of the solid solubility temperature T1 of this temperature and MnS and MnSe is roughly consistent.In addition, as shown in figure 27, also distinguish below with definite temperature corresponding to B content and carried out in the sample of heating of plate blank, obtain high magneticflux-density B8.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T3 of BN.That is, distinguish that it is effective not carrying out heating of plate blank in the temperature province of solid solution fully at MnS, MnSe and BN.
Similarly, studied relation between the condition of hot rolling and the epithelium adaptation behind the final annealing.This results are shown in Figure 28 and Figure 29.The X-coordinate of Figure 28 represents Mn content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).The X-coordinate of Figure 29 represents B content (quality %), the temperature of the heating of plate blank when ordinate zou represents hot rolling (℃).In addition, white circle expression epithelium adaptation improves, and black square represents to have produced epithelium to be peeled off, and the epithelium adaptation does not improve.In addition, solid solubility temperature T1(℃ of the MnS shown in two the curve representation formulas (2) among Figure 28) and solid solubility temperature T2(℃ of the MnSe shown in the formula (3)), solid solubility temperature T3(℃ of the BN shown in the curve representation formula (4) among Figure 29).As shown in figure 28, distinguish take the atmosphere of carrying out heating of plate blank, final annealing below the definite temperature corresponding to Mn content in the sample of appropriate condition, the epithelium adaptation improves.In addition, distinguish that also the solid solubility temperature T2 of the solid solubility temperature T1 of this temperature and MnS and MnSe is roughly consistent.In addition, as shown in figure 29, also distinguish take the atmosphere of carrying out heating of plate blank, final annealing below the definite temperature corresponding to B content in the sample of appropriate condition, the epithelium adaptation improves.In addition, distinguish that also this temperature is roughly consistent with the solid solubility temperature T3 of BN.That is, distinguish that it appropriately is effective fully not carrying out heating of plate blank, make the atmosphere of final annealing in the temperature province of solid solution at MnS, MnSe and BN.
And then, the Precipitation Characteristics of BN is studied, the result distinguishes that its Precipitation Temperature zone is 800 ℃～1000 ℃.
In addition, inventors of the present invention are studied the finish rolling end temp of hot rolling.In this research, at first, obtain following various blank plates of silicon steels: it contains Si:3.3 quality %, C:0.06 quality %, acid-solubility Al:0.026 quality %, N:0.009 quality %, Mn:0.1 quality %, S:0.005 quality %, Se:0.007 quality % and B:0.001 quality %～0.004 quality %, and remainder is made of Fe and inevitable impurity.Then, blank plates of silicon steels is heated under 1200 ℃ temperature, carry out hot rolling.Hot rolling is carried out roughing exactly under 1050 ℃, then carry out finish rolling under 1020 ℃～900 ℃, obtains the hot rolled strip that thickness is 2.3mm.Next, hot rolled strip shower cooling water is cooled to 550 ℃, then in atmosphere, cools off.Next, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, the speed heats cold strip rolling with 15 ℃/second carries out decarburizing annealing under 850 ℃ temperature, thereby obtains the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.021 quality %.Then, coating is with the annealing separation agent of MgO as main component, with the nitrogen partial pressure P of 800 ℃～1100 ℃ atmosphere N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1, with the nitrogen partial pressure P of the atmosphere more than 1100 ℃ N2Be made as below 0.1, with oxygen gesture Log[P H2O/ P H2] be made as-2 and carry out final annealing to get off, make various samples.
Next, the finish rolling end temp of hot rolling and the relation between the magnetic properties behind the final annealing have been studied.This results are shown in Figure 30.The X-coordinate of Figure 30 represents B content (quality %), and ordinate zou represents finish rolling end temp Tf.In addition, white circle expression magneticflux-density B8 is more than the 1.91T, and black square represents that magneticflux-density B8 is less than 1.91T.As shown in figure 30, distinguish in the situation that finish rolling end temp Tf satisfies formula (5), obtain high magneticflux-density B8.This thinks that separating out further of BN is promoted owing to the control by finish rolling end temp Tf.
Similarly, the finish rolling end temp of hot rolling and the relation between the epithelium adaptation behind the final annealing have been studied.This results are shown in Figure 31.The X-coordinate of Figure 31 represents B content (quality %), and ordinate zou represents finish rolling end temp Tf.In addition, white circle expression epithelium adaptation improves, and black square represents to produce epithelium to be peeled off, and the epithelium adaptation does not improve.As shown in figure 31, distinguish at finish rolling end temp Tf and satisfy in the situation of the appropriate condition of the atmosphere of formula (5), final annealing, the epithelium adaptation improves.
As previously discussed, by the 1st～the 3rd result who tests as can be known, by the atmosphere of separating out form and final annealing of control BN, can stably improve magnetic properties and the epithelium adaptation of grain-oriented magnetic steel sheet.In addition, in situation the about atmosphere of final annealing not being made as based on the value of formula (9) and (10), have excellent magnetic characteristics but do not obtain the effect of improving of epithelium adaptation.In the situation that B is not as BN and with MnS or MnSe is compound separates out, it is unstable that secondary recrystallization becomes, do not obtain good magnetic properties, in addition, now be not still not clear although can not occur the detailed reason of improving effect of epithelium adaptation when the atmosphere of final annealing not being controlled, can consider as follows.
At first, as described below about magnetic properties.Usually, the B of solid solution condition is easy to be segregated in a boundary, and the BN that separates out separately after hot rolling is more to be fine.Grain growing occurs in the B of these solid solution conditions and fine BN when being suppressed at primary recrystallization as the inhibitor of brute force in carrying out the low temperature zone of decarburizing annealing, become and can not play a role as inhibitor and divide at the high-temperature intra-zone that carries out final annealing, the grain structure of steel becomes duplex grain structure.Therefore, the primary recrystallization temperature is in the low temperature zone time, and the primary recrystallization grain is little, so the magneticflux-density step-down of grain-oriented magnetic steel sheet.In addition, grain structure becomes duplex grain structure in the high-temperature zone, so secondary recrystallization becomes unstable.
Then, as described below about the epithelium adaptation.At first, exist as oxide compound about the B that purifies the state of the B after annealing, can think on the interface that is present between glass epithelium and the steel plate.Although can think that purifying previous crops be that BN exists, by purification BN is decomposed, the B in the steel plate diffuses to the surface near steel plate, forms oxide compound.Although the details of oxide compound is still not clear, inventors of the present invention infer that Mg, Si, the Al in the root that is present in glass epithelium and glass epithelium formed composite oxides.
BN makes B at the surface enrichment of steel plate in the later half decomposition of final annealing, if but the enrichment of B occurs in the formation initial stage of glass epithelium, and the interface structure after then final annealing finishes is that B is in the part enrichment more shallow than the root of glass epithelium.Therefore, can't form and have the such material of feature of the present invention.On the other hand, under BN begins to decompose under the state to a certain degree situation has been carried out in the formation of glass epithelium, near the B enrichment root of glass epithelium, the interface formation of glass epithelium and steel plate has the structure of feature of the present invention.Herein, it is the situation that the formation of the root of glass epithelium has begun that state has to a certain degree been carried out in the formation of glass epithelium, and this temperature province is roughly more than 1000 ℃.Therefore, in order to realize the interface structure between glass epithelium of the present invention and steel plate, can be made as B this can enrichment more than temperature condition, can be to stable existence till the high temperature but therefore need to be arranged in the BN precipitate of steel plate.
BN is fine and not with MnS or MnSe is compound when separating out, decomposition temperature in the final annealing reduces, the B of solid solution is the just interface enrichment between glass epithelium and steel plate when the root of glass epithelium does not form, and can not help the anchoring effect at the interface between glass epithelium and the steel plate to improve.Therefore, can think that the raising effect of epithelium adaptation becomes and do not had.
So, effectively play a role in order to make B, need to control in high-temperature portion the atmosphere of final annealing.In order to achieve, inventors find to arrange the decomposition that suppresses BN until 800 ℃～1100 ℃ and promoting the decomposition of BN more than 1100 ℃, promoting that the atmosphere that purifies is effective simultaneously.
In addition because B also uses as the additive of annealing separation agent, therefore sometimes in the grain-oriented magnetic steel sheet that has experienced final annealing the near interface between glass epithelium and steel plate observe the segregation of B.Yet being used for the B of self-annealing separating agent, to obtain glass epithelium and the interface structure between the steel plate that the present invention has be very difficult.For the B that is used to the self-annealing separating agent realizes the such enrichment situation of interface structure between glass epithelium of the present invention and the steel plate, need to be from the surface of steel plate to steel plate the B of diffusion q.s.Can think B oxide compound since in the element that consists of the glass epithelium equilibrium solution tripping of oxygen higher, therefore be difficult for causing the situation that the root of comparing the low glass epithelium of oxygen gesture with the top layer of glass epithelium forms oxide compound that is presumed to that diffuses to.So the B that is used to the self-annealing separating agent realizes that glass epithelium and the interface structure between the steel plate that the present invention has are very difficult.
Then, the reason that just each condition of the present invention is limited below describes.
At first, about the interface structure between glass epithelium and the steel plate, if the enrichment position in deep of B is darker than the enrichment position of Mg, then the adaptation of glass epithelium improves.In the situation of being carried out the GDS analysis by the surface of glass epithelium, be made as tB(second to represent discharge time in the peak position with the deep of the enrichment of B), the peak position of Mg is made as tMg(second) time, if above-mentioned value reaches following condition then can obtain good result.
tMg×1.6≤tB≤tMg×5?（1）
On the other hand, when the tB value is excessive, the tendency of magnetic properties variation is arranged.Therefore, the tB value is made as tMg * 5.0 when following, preferred.
Then, the restriction reason of the atmosphere of final annealing described.Between 800 ℃～1100 ℃ with nitrogen partial pressure P N2Remain on 0.75～0.2, and with oxygen gesture Log[P H2O/ P H2] be made as-below 0.7.This is owing to the decomposition of BN in 800～1100 ℃ temperature province can be inhibited.If do not suppress the decomposition of BN in this temperature province, then becoming to obtain good adaptation.Its reason is: if can't fully suppress the decomposition of BN in the inappropriate situation of atmosphere, then B is from the early stage surface diffusion to steel plate of final annealing, in the surperficial shallow position enrichment of distance steel plate.
The detailed content of the condition of the atmosphere of final annealing is as described below.That is, nitrogen partial pressure P N2Be made as the value more than 0.2 for the decomposition of moderate inhibition BN.On the other hand, in the situation that surpass 0.75 and too high, extra-inhibitory BN decomposition and can not produce good secondary recrystallization.In addition, oxygen gesture Log[P H2O/ P H2] surpassing the oxidation that can produce B at-0.7 o'clock, the result can promote the decomposition of BN.Therefore, in order to be suppressed at the decomposition of BN in 800～1100 ℃ the temperature province, the atmosphere of final annealing will satisfy the nitrogen partial pressure P in upper explanation N2And oxygen gesture Log[P H2O/ P H2] condition.
In addition, about the control of the atmosphere of final annealing, if according to (11) formula oxygen partial pressure and nitrogen partial pressure are controlled, then can obtain better result.
4Log[P N2]=3Log[P H2O/P H2]+A+3455/T?（11）
Herein ,-3.72 〉=3Log[P H2O/ P H2]+A 〉=-5.32 and-0.7 〉=Log[P H2O/ P H2], T represents absolute temperature.
In addition, the temperature province that is made as above-mentioned atmospheric condition is 800 ℃～1100 ℃.Under than 800 ℃ of lower temperature, the initial temperature region overlapping with the formation of glass epithelium is made as above-mentioned oxygen gesture Log[P in this field H2O/ P H2] time, the glass epithelium that can't obtain perfecting brings detrimentally affect might for the epithelium adaptation.Because lower limit temperature is crossed when low the decomposition that can bring detrimentally affect to adaptation, can't fully suppress BN when too high, therefore in the present embodiment, lower limit temperature is made as 800 ℃.On the other hand, during the excess Temperature of the upper limit, it is unstable that secondary recrystallization becomes, and ceiling temperature is crossed when low, B easily be concentrated in surface of steel plate extremely near, might lose the effect that improves adaptation.Therefore, in the present embodiment, between 800 ℃ to 1100 ℃, realize the atmosphere of above-mentioned condition.
About the control method of the atmosphere of final annealing, for nitrogen partial pressure P N2, can be by nitrogen and hydrogen etc. not be controlled to realize with the ratio of mixture of the gas of steel plate reaction.In addition, for oxygen gesture Log[P H2O/ P H2], dew point that can be by controlled atmosphere etc. is realized.
In addition, in surpassing 1100 ℃ the atmosphere of temperature, preferably with nitrogen partial pressure P N2When being made as below 0.1 with oxygen gesture Log[P H2O/ P H2] be made as-below 2.This is for the position in regulation makes B as the oxide compound enrichment, further carries out the purification behind the secondary recrystallization.With oxygen gesture Log[P H2O/ P H2] the upper limit be made as-2 reason be for make B as oxide compound in the further enrichment of the near surface of steel plate.This is worth when too high, and the enrichment of B oxide compound occurs in the steel plate deep, becomes to obtain good magnetic properties.In addition, with nitrogen partial pressure P N2The reason that is made as below 0.1 is nitrogen partial pressure P N2The enrichment meeting of B oxide compound occurs near the surface of steel plate when too high, and becoming to obtain good adaptation.In addition, sometimes also because be difficult to purify, annealing time can become long and uneconomical.As described above in detail, effectively play a role to improve the epithelium adaptation in order to make B, need to be to the nitrogen partial pressure P in the high-temperature area in final annealing N2With oxygen gesture Log[P H2O/ P H2] control.
Then, the restriction reason of composition range described.
The employed silicon steel starting material of present embodiment contain Si:0.8 quality %～7 quality %, acid-solubility Al:0.01 quality %～0.065 quality %, N:0.004 quality %～0.012 quality %, Mn:0.05 quality %～1 quality %, S and Se: by total amount 0.003 quality %～0.015 quality % and B:0.0005 quality %～0.0080 quality %, C content is below the 0.085 quality %, and remainder is made of Fe and inevitable impurity.
In addition, the grain-oriented magnetic steel sheet that finally obtains contains the Mn of Si, the 0.05 quality %～1 quality % of 0.8 quality %～7 quality %, the B of 0.0005 quality %～0.0080 quality %, the content of Al, C, N, S and Se is respectively below the 0.005 quality %, and remainder is made of Fe and inevitable impurity.
Si improves resistance and reduces iron loss.Yet, when Si content surpasses 7 quality %, the cold rolling very difficulty that becomes, becoming when cold rolling easily cracks.Therefore, Si content is made as below the 7 quality %, is preferably below the 4.5 quality %, more preferably below the 4 quality %.In addition, Si content produces the γ phase transformation less than 0.8 quality % the time when final annealing, can damage the crystalline orientation of grain-oriented magnetic steel sheet.Therefore, Si content is made as more than the 0.8 quality %, is preferably more than the 2 quality %, more preferably more than the 2.5 quality %.
C organizes effective element to control primary recrystallization, but can bring detrimentally affect to magnetic properties.Therefore, in the present embodiment, before final annealing, carry out decarburizing annealing.Yet when C content surpassed 0.085 quality %, the time that decarburizing annealing spends was elongated, can damage the productivity in the industrial production.Therefore, C content is made as below the 0.085 quality %, is preferably below the 0.07 quality %.
In addition, can bring detrimentally affect to magnetic properties when C surpasses 0.005 quality % in the grain-oriented magnetic steel sheet that finally obtains, the C content in the grain-oriented magnetic steel sheet that therefore finally obtains is made as below the 0.005 quality %.
Acid-solubility Al is combined with N and is separated out as (Al, Si) N, thereby plays a role as inhibitor.In the situation in the content of acid-solubility Al is in the scope of 0.01 quality %～0.065 quality %, secondary recrystallization is stable.Therefore, the content of acid-solubility Al is made as more than the 0.01 quality % and below the 0.065 quality %.In addition, the content of acid-solubility Al is preferably more than the 0.02 quality %, more preferably more than the 0.025 quality %.In addition, the content of acid-solubility Al is preferably below the 0.04 quality %, more preferably below the 0.03 quality %.
In addition, can bring detrimentally affect to magnetic properties when surpassing 0.005 quality % owing to Al in the grain-oriented magnetic steel sheet that finally obtains, the Al content in the grain-oriented magnetic steel sheet that therefore finally obtains is made as below the 0.005 quality %.
B is combined as BN and with MnS with N or MnSe is compound separates out, thereby plays a role as inhibitor.In the situation in B content is in the scope of 0.0005 quality %～0.0080 quality %, secondary recrystallization is stable.Therefore, B content is made as more than the 0.0005 quality % and below the 0.0080 quality %.In addition, B content is preferably more than the 0.001 quality %, more preferably more than the 0.0015 quality %.In addition, B content is preferably below the 0.0040 quality %, more preferably below the 0.0030 quality %.
In addition, in the grain-oriented magnetic steel sheet that finally obtains by having added B from annealing separation agent etc.Owing to can bring detrimentally affect to magnetic properties when B ultrasonic is crossed 0.0080 quality %, the B content in the grain-oriented magnetic steel sheet that therefore finally obtains is made as 0.0005 quality %～0.0080 quality %.
N is combined with B or Al and is played a role as inhibitor.N content can't obtain the inhibitor of q.s during less than 0.004 quality %.Therefore, N content is made as more than the 0.004 quality %, is preferably more than the 0.006 quality %, more preferably more than the 0.007 quality %.On the other hand, when N content surpasses 0.012 quality %, in steel band, can produce the emptying aperture that is called as bubble (blister) when cold rolling.Therefore, N content is made as below the 0.012 quality %, is preferably below the 0.010 quality %, more preferably below the 0.009 quality %.
In addition, can bring detrimentally affect to magnetic properties when N surpasses 0.005 quality % in the grain-oriented magnetic steel sheet that finally obtains, the N content in the grain-oriented magnetic steel sheet that therefore finally obtains is made as below the 0.005 quality %.
Mn, S and Se generate MnS and the MnSe as the compound nuclear of separating out of BN, thereby miscible precipitate plays a role as inhibitor.Mn content is in the situation in the scope of 0.05 quality %～1 quality %, and secondary recrystallization is stable.Therefore, Mn content is made as more than the 0.05 quality % and below the 1 quality %.In addition, Mn content is preferably more than the 0.08 quality %, more preferably more than the 0.09 quality %.In addition, Mn content is preferably below the 0.50 quality %, more preferably below the 0.2 quality %.
In addition, when Mn departs from the scope of 0.05 quality %～1 quality % in the grain-oriented magnetic steel sheet that finally obtains, it is unstable that secondary recrystallization becomes, and can bring detrimentally affect to magnetic properties, and the Mn content of the grain-oriented magnetic steel sheet that therefore finally obtains is made as 0.05 quality %～1 quality %.
In addition, under the content of S and Se was in by the situation in the scope of total amount 0.003 quality %～0.015 quality %, secondary recrystallization was stable.Therefore, the content of S and Se is made as more than the 0.003 quality % by total amount and below the 0.015 quality %.In addition, the viewpoint of the generation of crackle is considered from prevent hot rolling, preferably satisfies following formula (14).In addition, can in the silicon steel starting material, only contain any element among S or the Se, also can contain these two kinds of elements of S and Se.In the situation that contain S and these two kinds of elements of Se, can promote more stably that BN's separates out, stably improves magnetic properties.
[Mn]/([S]+[Se])≥4?（14）
In addition, can bring detrimentally affect to magnetic properties when S and Se surpass 0.005 quality % in the grain-oriented magnetic steel sheet that finally obtains, the S of the grain-oriented magnetic steel sheet that therefore finally obtains and the content of Se are made as below the 0.005 quality %.
Ti forms thick TiN, and the volume production of separating out that can reach to the BN that plays a role as inhibitor (Al, Si) N is given birth to impact.When Ti content surpasses 0.004 quality %, be difficult to obtain good magnetic properties.Therefore, Ti content is preferably below the 0.004 quality %.
In the silicon steel starting material, can further contain among Cr, Cu, Ni, P, Mo, Sn, Sb and the Bi more than one in following scope.
Cr can improve the zone of oxidation that forms when decarburizing annealing, be effective to the formation of glass epithelium.Yet, when Cr content surpasses 0.3 quality %, can significantly hinder decarburization.Therefore, Cr content is made as below the 0.3 quality %.
Cu improves resistivity and reduces iron loss.Yet when Cu content surpassed 0.4 quality %, this effect can be saturated.In addition, in the situation that hot rolling also produces the surface spots that is called as " copper whisker " sometimes.Therefore, Cu content is made as below the 0.4 quality %.
Ni improves resistivity and reduces iron loss.In addition, Ni controls the metal structure of hot rolled strip and improves magnetic properties.Yet when Ni content surpassed 1 quality %, it is unstable that secondary recrystallization becomes.Therefore, Ni content is made as below the 1 quality %.
P improves resistivity and reduces iron loss.Yet, when P content surpasses 0.5 quality %, can have problems on the rolling property.Therefore, P content is made as below the 0.5 quality %.
Surface texture when Mo improves hot rolling.Yet when Mo content surpassed 0.1 quality %, this effect can be saturated.Therefore, Mo content is made as below the 0.1 quality %.
Sn and Sb are the grain boundary segregation element.Because the employed silicon steel starting material of present embodiment contain Al, therefore according to the sometimes Al moisture oxidation that can be discharged from annealing separation agent of the condition of final annealing.In this case, different according to the position in the grain-oriented magnetic steel sheet, inhibitor intensity produces uneven, and also there is inequality in magnetic properties sometimes.Yet, in the situation that contain the grain boundary segregation element, can suppress the oxidation of Al.That is, the oxidation of Sn and Sb inhibition Al suppresses the inequality of magnetic properties.But, when the content of Sn and Sb surpasses 0.30 quality % by total amount, when decarburizing annealing, being difficult to form zone of oxidation, the formation of glass epithelium becomes insufficient.In addition, can significantly hinder decarburization.Therefore, the content of Sn and Sb is made as below the 0.3 quality % by total amount.
Bi makes the precipitate of sulfide etc. become stable and strengthens function as inhibitor.Yet, when Bi content surpasses 0.01 quality %, bring detrimentally affect for the formation of glass epithelium.Therefore, Bi content is made as below the 0.01 quality %.
Then, each processing in the present embodiment is described.
The silicon steel starting material (slab) of mentioned component are such as making by following method: come steel-smelting with converter or electric furnace etc., and as required molten steel is carried out Fruit storage, then cast continuously.In addition, also can replace the continuous casting, carry out ingot casting after split rolling method make.The thickness of blank plates of silicon steels for example is made as 150mm～350mm, preferably is made as 220mm～280mm.In addition, can make the so-called thin slab that thickness is 30mm～70mm.In the situation that make thin slab, can omit the roughing when obtaining hot rolled strip.
After the making of blank plates of silicon steels, carry out heating of plate blank, carry out hot rolling.Next, in the present embodiment, make that BN and MnS and/or MnSe are compound to separate out, satisfy following formula (the 6)～mode of (8) by the amount of separating out of the BN in the hot rolled strip, MnS and MnSe and set the condition of heating of plate blank and hot rolling.
B asBN≥0.0005?（6）
[B]-B asBN≤0.001?（7）
S asMnS+0.5×Se asMnSe≥0.002?（8）
Herein, " B AsBN" amount (quality %) of the B that separates out as BN of expression, " S AsMnS" amount (quality %) of the S that separates out as MnS of expression, " Se AsMnSe" amount (quality %) of the Se that separates out as MnSe of expression.
B is controlled its amount of separating out and solid solution capacity by the mode that satisfies formula (6) and formula (7).In order to ensure the amount of inhibitor, a certain amount of above BN is separated out.In addition, under the susceptible condition of amount of the B of solid solution, in operation thereafter, form unsettled nano-precipitation sometimes and bring detrimentally affect to the primary recrystallization tissue.
MnS and MnSe are as the compound nuclear performance function of separating out of BN.Therefore, fully separate out the raising magnetic properties in order to make BN, control its amount of separating out by the mode that satisfies formula (8).
Condition shown in the formula (6) is the condition that is derived by Fig. 4, Figure 14 and Figure 24.By Fig. 4, Figure 14, and Figure 24 as can be known, at [B]-B AsBNBe in the following situation of 0.001 quality %, obtaining magneticflux-density B8 is the above good magneticflux-density of 1.88T.
Condition shown in formula (6) and the formula (8) is the condition that is derived by Fig. 2, Figure 12 and Figure 22.As shown in Figure 2, at B AsBNBe more than the 0.0005 quality % and S AsMnSBe in the above situation of 0.002 quality %, obtaining magneticflux-density B8 is the above good magneticflux-density of 1.88T.
Similarly, as shown in Figure 12, at B AsBNBe more than the 0.0005 quality % and Se AsMnSeBe in the above situation of 0.004 quality %, obtaining magneticflux-density B8 is the above good magneticflux-density of 1.88T.Similarly, as shown in Figure 22, at B AsBNBe more than the 0.0005 quality % and S AsMnS+ 0.5 * Se AsMnSeBe in the above situation of 0.002 quality %, obtaining magneticflux-density B8 is the above good magneticflux-density of 1.88T.Next, S AsMnSBe 0.002 quality % when above, S AsMnS+ 0.5 * Se AsMnSeMust be for more than the 0.002 quality %, Se AsMnSeBe 0.004 quality % when above, S AsMnS+ 0.5 * Se AsMnSeMust be for more than the 0.002 quality %.Therefore, S AsMnS+ 0.5 * Se AsMnSeBe to be important more than the 0.002 quality %.
In addition, the temperature of heating of plate blank is set by the mode that satisfies following condition.
(i) in the situation that contain S and Se in the blank plates of silicon steels
The temperature of heating of plate blank is made as temperature T 1(℃ shown in the formula (2)) temperature T 2(℃ shown in following, the formula (3)) temperature T 3(℃ shown in the following and formula (4)) below;
(ii) in the situation that do not contain Se in the blank plates of silicon steels
The temperature of heating of plate blank is made as temperature T 1(℃ shown in the formula (2)) temperature T 3(℃ shown in the following and formula (4)) below;
(iii) in the situation that do not contain S in the blank plates of silicon steels
The temperature of heating of plate blank is made as temperature T 2(℃ shown in the formula (3)) temperature T 3(℃ shown in the following and formula (4)) below;
T1=14855/(6.82-log([Mn]×[S]))-273?（2）
T2=10733/(4.08-log([Mn]×[Se]))-273?（3）
T3=16000/(5.92-log([B]×[N]))-273?（4）
If this is owing to carrying out heating of plate blank with such temperature, then not fully solid solution of BN, MnS and MnSe when heating of plate blank, and can promote BN, MnS and MnSe in hot rolling, to separate out.As by Fig. 6, Figure 16 and Figure 26 as can be known, the upper limit of the slab heating temperature of the magneticflux-density B8 that solid solubility temperature T1 and T2 and acquisition 1.88T are above is roughly consistent.In addition, as by Fig. 7, Figure 17 and Figure 27 as can be known, the upper limit of the slab heating temperature of the magneticflux-density B8 that solid solubility temperature T3 is above with obtaining 1.88T is roughly consistent.
In addition, further preferably by the mode that also satisfies following condition the temperature of heating of plate blank is set.This is to separate out for the MnS that makes preferred amounts in heating of plate blank or MnSe.
(i) in the situation that do not contain Se in the blank plates of silicon steels
Shown in the following formula (15) temperature T 4(℃) below;
(ii) in the situation that do not contain S in the blank plates of silicon steels
The temperature of heating of plate blank is made as temperature T 5(℃ shown in the following formula (16)) below;
T4=14855/(6.82-log([Mn-0.0034]×[S-0.002]))-273?（15）
T5=10733/(4.08-log([Mn-0.0034]×[Se-0.004]))-273?（16）
In the excess Temperature situation of heating of plate blank, BN, MnS and/or MnSe can complete solid solutions sometimes.In this case, make BN, MnS and/or MnSe when hot rolling, separate out difficult.Therefore, heating of plate blank preferably with temperature T 1 and/or temperature T below 2 and temperature T carry out below 3.In addition, the temperature of heating of plate blank is temperature T 4 or T5 when following, and MnS or the MnSe that can separate out preferred amounts in heating of plate blank therefore can be at the compound BN that separates out of they peripheries, thereby can easily form effective inhibitor.
In addition, for B, satisfy the mode of following formula (5) by the finish rolling end temp Tf in hot rolling and set.This is in order further to promote separating out of BN.
Tf≤1000-10000×[B]?（5）
As Figure 10, Figure 20, Figure 30 as can be known, the condition of the magneticflux-density B8 that the condition shown in the formula (5) is above with obtaining 1.88T is roughly consistent.In addition, consider from the viewpoint of separating out of BN, finish rolling end temp Tf further preferably is made as more than 800 ℃.
After hot rolling, hot rolled strip is annealed.Then, carry out cold rolling.As mentioned above, cold rolling can only carrying out once also can carry out repeatedly cold rolling when process annealing is carried out in the centre.In cold rolling, preferably final cold rolling rate is made as more than 80%.This is in order to make good primary recrystallization texture flourishing.
Then, carry out decarburizing annealing.Consequently, the contained C of steel band is removed.Decarburizing annealing is for example carried out in moistening atmosphere.In addition, for example preferred so that the crystal particle diameter that obtains by primary recrystallization in 770 ℃～950 ℃ temperature province becomes the time such more than the 15 μ m carries out.This is in order to obtain good magnetic properties.Next, carry out coating and the final annealing of annealing separation agent.Consequently, by secondary recrystallization, the crystal grain of { 110 }＜001＞orientation can preferred growth.
In addition, manifest to the final annealing from beginning decarburizing annealing secondary recrystallization during, carry out nitriding treatment.This is in order to form the inhibitor of (Al, Si) N.This nitriding treatment can carry out in decarburizing annealing, also can carry out in final annealing.When in decarburizing annealing, carrying out, as long as in the atmosphere that contains the gas that has the nitrogenize ability such as ammonia etc., anneal.In addition, can be in the heating zone of continuous annealing furnace or any stage in the soaking zone carry out nitriding treatment, in addition, also can the stage after leaning on than the soaking zone carry out nitriding treatment.When in final annealing, carrying out nitriding treatment, as long as the powder that has the nitrogenize ability such as MnN etc. is added in the annealing separation agent.
With regard to the method for final annealing, as mentioned above, temperature is 800 ℃～1100 ℃ temperature range, and atmosphere satisfies (9) and (10) formula.
0.75≥P N2≥0.2?（9）
-0.7≥Log[P H2O/P H2]?（10）
Therefore final annealing can reach the condition of (9) formula owing to common mixed atmosphere by nitrogen and hydrogen carries out by the nitrogen partial pressure of controlling this atmosphere.In addition, the oxygen gesture can contain water vapour and controls by making in the atmosphere, can make it satisfy the condition of (10) formula.
When the condition that further satisfies (11) formula and the atmosphere more than 1100 ℃ satisfy formula (12) and (13), can obtain better result herein.
4Log[P N2]=3Log[P H2O/P H2]+A+3455/T?（11）
0.1≥P N2?（12）
-2≥Log[P H2O/P H2]?（13）
Herein ,-3.72 〉=3Log[P H2O/ P H2]+A 〉=-5.32 and-0.7 〉=Log[P H2O/ P H2], P N2The expression nitrogen partial pressure, P H2O, P H2Represent respectively steam partial pressure, hydrogen dividing potential drop, A is for pressing based on Log[P H2O/ P H2] make 3Log[P H2O/ P H2]+A enters the definite constant of mode of the scope of regulation, and T represents absolute temperature.
In the present embodiment, owing to having strengthened inhibitor by BN, therefore in the heat-processed of final annealing, preferably the rate of heating in 1000 ℃～1100 ℃ temperature range is made as below 15 ℃/hour.In addition, replace the control of rate of heating, it also is effective keeping the cycle annealing more than 10 hours in 1000 ℃～1100 ℃ temperature range.
According to such present embodiment, can stablize the grain-oriented magnetic steel sheet of making excellent magnetic properties.
Embodiment
Then, the test that inventors of the present invention carried out is described.Condition in these tests etc. is the example that adopts in order to confirm exploitativeness of the present invention and effect, and the present invention is not subjected to the restriction of these examples.
＜embodiment 1＞
Making has such composition as described in Table 1 and remainder by Fe and the inevitable slab that consists of of impurity.Then, at 1100 ℃ of lower heating slabs, then under 900 ℃, carry out finish rolling.In addition, 1100 ℃ Heating temperature all is the value that is lower than the value of the temperature T 1 that calculated by forming of table 1, T2, T3.Carry out in this wise and obtain the hot rolled strip that thickness is 2.3mm.Next, under 1100 ℃, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, in 830 ℃ moistening atmosphere gas, carry out the decarburizing annealing in 100 seconds, thereby obtain the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, make the nitrogen in the steel band increase to 0.023 quality %.Then, be coated with the annealing separation agent of MgO as main component the nitrogen partial pressure P of near 800 ℃ atmosphere N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-0.5, with the nitrogen partial pressure P of 800 ℃～1100 ℃ atmosphere N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1, with the nitrogen partial pressure P of the atmosphere more than 1100 ℃ N2Be made as below 0.1, with oxygen gesture Log[P H2O/ P H2] be made as-below 2, be heated to 1200 ℃ with 15 ℃/hour speed and carry out final annealing.
The steel plate that carries out in this wise and obtain has the composition shown in the table 2.To the sample behind such final annealing, measure situation and the magnetic properties (magneticflux-density B8) of epithelium.At first, about the situation of epithelium, studied the ratio of the forsterite in the glass epithelium and based on the peak position of Mg and the B of GDS.In addition, before measuring by GDS, making by solid component concentration is that 50% phosphate dihydrogen aluminum solution 100g, solid component concentration are the coating fluid that 20% colloid silica 102g and chromic trioxide 5.4g form.Next, be 5g/m to the steel plate with glass epithelium behind the final annealing by the rear single face of baking 2Mode be coated with coating fluid and dry, then 900 ℃ of lower bakings.The thickness of secondary epithelium in this case is 1.5 μ m.
In addition, magnetic properties (magneticflux-density B8) is measured according to JIS C2556.Further, also by following step the epithelium adaptation is tested.At first, making by solid component concentration is that 50% phosphate dihydrogen aluminum solution 100g, solid component concentration are the coating fluid that 20% colloid silica 102g and chromic trioxide 5.4g form.Next, be 10g/m to the steel plate with glass epithelium behind the final annealing by the rear single face of baking 2Mode be coated with coating fluid and dry, then 900 ℃ of lower bakings.Then, this steel plate is wound to the pole of diameter 20 φ, the inboard steel plate that then is determined at curved part exposes the area of peeling off of such epithelium.Peel off area and be 5% when following, be judged as adaptation good.Above test the results are shown in table 3.
Table 1
Figure BDA00003502746800321
Table 2
Figure BDA00003502746800322
Table 3
Figure BDA00003502746800331
Shown in table 2 and table 3, be that tB/tMg is in the situation of the slab more than 1.6 more than 70% and with regard to the peak position of the Mg in the GDS curve and B in the forsterite amount for the steel plate of the composition of scope of the present invention and glass epithelium as can be known, adaptation and magneticflux-density are good.Especially tB/tMg is 2.0 when above, and particularly adaptation is good.On the other hand, because magnetic properties surpasses 5.0 o'clock variation at tB/tMg, so tB/tMg is take 5 as the upper limit.The forsterite amount in the amount of Si and Al not in the situation that scope of the present invention can't be guaranteed the amount more than 70%.
＜embodiment 2＞
Making has composition in the table 4 and remainder by Fe and the inevitable slab that consists of of impurity.Further carry out heating of plate blank and finish rolling with the temperature condition in the table 5, obtain the hot rolled strip that thickness is 2.3mm.The analytical results that has passed through B, BN, MnS and MnSe that so heat treated heat prolongs plate is as shown in table 6.Next, under 1100 ℃, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, in 830 ℃ moistening atmosphere gas, carry out the decarburizing annealing in 100 seconds, thereby obtain the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.023 quality %.Then, coating arranges to 800 ℃ atmosphere, with the nitrogen partial pressure P of 800 ℃～1100 ℃ atmosphere similarly to Example 1 with the annealing separation agent of MgO as main component N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1, with the nitrogen partial pressure P of the atmosphere more than 1100 ℃ N2Be made as below 0.1, with oxygen gesture Log[P H2O/ P H2] be made as-below 2, be heated to 1200 ℃ with 15 ℃/hour speed and carry out final annealing.Next, similarly to Example 1, carry out the evaluation based on tB and the tMg of GDS, further measure magnetic properties (magneticflux-density B8).In addition, also carried out the test of epithelium adaptation.This results are shown in table 7.
Table 4
Figure BDA00003502746800341
Table 5
Figure BDA00003502746800351
Table 6
Figure BDA00003502746800352
Table 7
Figure BDA00003502746800361
As shown in table 7, in the situation that test No.d1～test No.d3, because slab heating temperature is higher than T1, so the epithelium adaptation is poor, and magneticflux-density is also low.In addition, in the situation that test No.d4, because finish rolling end temp Tf is higher than 1000-10000 * [B], so the epithelium adaptation is poor.In addition, in the situation that test No.d5, because finish rolling end temp Tf is lower than 800 ℃, so the epithelium adaptation is poor, and magneticflux-density is also low.In the situation that test No.d6, d7, because slab heating temperature is higher than T1, T3, and B AsBNLess than 0.0005, and [B]-B AsBNSurpass 0.001, so the epithelium adaptation is poor, magneticflux-density is also low.In the situation that test No.d8, because S AsMnS+ Se AsMnSeValue less than 0.002, so magneticflux-density is low.On the other hand, compare with temperature T 1, T2 and T3 at slab heating temperature in the situation of the low following test No.D1 as example of slab heating temperature～test No.D10, obtain good epithelium adaptation and magneticflux-density.
As by the above as can be known, according to the operating condition of scope of the present invention, can access the grain-oriented magnetic steel sheet with good magnetic properties and epithelium adaptation.
＜embodiment 3＞
Making has composition in the table 8 and remainder by Fe and the inevitable slab that consists of of impurity.Then, with the heating of the condition in the table 9 slab, then under 900 ℃, carry out finish rolling.Carry out in this wise and obtain the hot rolled strip that thickness is 2.3mm.Next, under 1100 ℃, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, in 830 ℃ moistening atmosphere gas, carry out the decarburizing annealing in 100 seconds, thereby obtain the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.022 quality %.Then, coating arranges to 800 ℃ atmosphere, with the nitrogen partial pressure P of 800 ℃～1100 ℃ atmosphere similarly to Example 1 with the annealing separation agent of MgO as main component N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1, with the nitrogen partial pressure P of the atmosphere more than 1100 ℃ N2Be made as below 0.1, with oxygen gesture Log[P H2O/ P H2] be made as-2, be heated to 1200 ℃ with 15 ℃/hour speed and carry out final annealing.Next, similarly to Example 1, carry out the evaluation based on tB and the tMg of GDS, further measure epithelium adaptation and magnetic properties (magneticflux-density B8).This results are shown in table 10.
Table 8
Figure BDA00003502746800371
Table 9
Figure BDA00003502746800381
Table 10
Figure BDA00003502746800391
As by table 8 and table 10 as can be known, in the comparative example of raw-material Composition deviation scope of the present invention, the epithelium adaptation is poor, and magneticflux-density is low.Yet raw-material composition is in the example E1 of scope of the present invention～E23 and has obtained good epithelium adaptation and magneticflux-density.
＜embodiment 4＞
Take the test of research below the impact of the atmosphere under 800 ℃～1100 ℃ and switching temperature has been carried out as purpose.At first, make and to have the composition that contains Si:3.4 quality %, B:0.0025 quality %, C:0.06 quality %, N:0.008 quality %, S:0.007 quality %, Al:0.03 quality % and remainder by Fe and the inevitable slab that consists of of impurity.Then, at 1100 ℃ of lower heating slabs, then under 900 ℃, carry out finish rolling.Under 1100 ℃, all be to be lower than the value that forms the value of the temperature T 1 that calculates, T2, T3 by above-mentioned.Carry out in this wise and obtain the hot rolled strip that thickness is 2.3mm.Next, under 1100 ℃, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, in 830 ℃ moistening atmosphere gas, carry out the decarburizing annealing in 100 seconds, thereby obtain the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.023 quality %.Then, coating is with the annealing separation agent of MgO as main component, atmosphere to the temperature of the A1 of table 11 arranges similarly to Example 1, and is made as the atmosphere in the table 11 under the switching temperature A1 in table 11 and the A2, under the temperature higher than temperature A2 with nitrogen partial pressure P N2Be made as 0.05, with oxygen gesture Log[P H2O/ P H2] be made as-below 2, be heated to 1200 ℃ with 15 ℃/hour speed, carry out final annealing reaching after 1200 ℃ under hydrogen is 100% atmosphere.
To the sample behind such final annealing, measure situation and the magnetic properties (magneticflux-density B8) of epithelium.At first, about the situation of epithelium, the forsterite amount of glass epithelium and the Mg that is obtained by GDS and the peak position of B have been studied.The forsterite amount all is more than 70%.Making before the mensuration of GDS by solid component concentration is that 50% phosphate dihydrogen aluminum solution 100g, solid component concentration are the coating fluid that 20% colloid silica 102g and chromic trioxide 5.4g form.Next, be 5g/m to the steel plate with glass epithelium behind the final annealing by the rear single face of baking 2Mode be coated with coating fluid and dry, then 900 ℃ of lower bakings.The thickness of secondary epithelium in this case is 1.5 μ m.
In addition, magnetic properties (magneticflux-density B8) is measured according to JIS C2556.Further, also by following step the epithelium adaptation is tested.At first, making by solid component concentration is that 50% phosphate dihydrogen aluminum solution 100g, solid component concentration are the coating fluid that 20% colloid silica 102g and chromic trioxide 5.4g form.Next, be 10g/m to the steel plate with glass epithelium behind the final annealing by the rear single face of baking 2Mode be coated with coating fluid and dry, then 900 ℃ of lower bakings.This steel plate is wound to the pole of diameter 20 φ, the inboard steel plate that then is determined at curved part exposes the area of peeling off of such epithelium.Peel off area and be 5% when following, be judged as adaptation good.Above test the results are shown in table 11.
Table 11
Figure BDA00003502746800411
As shown in table 11, in the situation that test No.f1, because the nitrogen partial pressure P under 800 ℃～1100 ℃ N2Therefore cross lowly, carry out the decomposition of BN, B is in the near surface enrichment, and ratio tB/tMg diminishes, and does not obtain the raising effect of epithelium adaptation.In addition, in the situation that test No.f2, because nitrogen partial pressure P N2Too high, although therefore the epithelium adaptation is good, do not obtain good magnetic properties.In the situation that test No.f3, because oxygen gesture Log[P H2O/ P H2] too high, the decomposition and the magneticflux-density B8 that therefore carry out BN are poor, and in addition, ratio tB/tMg becomes too small, does not have the effect of improving of epithelium adaptation.
On the other hand, in the test No.f4 that has changed the atmosphere switching temperature, because switching temperature A1 is excessively low, does not therefore obtain adaptation and improve effect.In test No.f5, because switching temperature A1 is too high, therefore based on the decomposition of the oxidation of BN in advance, ratio tB/tMg becomes inappropriate value, and magneticflux-density B8 is also poor.In test No.f6, because switching temperature A2 is excessively low, so the decomposition of BN in advance, and ratio tB/tMg becomes inappropriate value, and magneticflux-density B8 is also poor.In test No.f7, because switching temperature A2 is too high, so the decomposition of BN delay, ratio tB/tMg is excessive, and magnetic properties is poor.
As by the above as can be known, if be made as operating condition of the present invention, then can access the grain-oriented magnetic steel sheet with good magnetic properties and epithelium adaptation.
＜embodiment 5＞
With the purpose of the better condition of studying the atmosphere under 800 ℃～1100 ℃, carried out following test.At first, make and to have the composition that contains Si:3.4 quality %, B:0.0025 quality %, C:0.06 quality %, N:0.008 quality %, S:0.007 quality %, Al:0.03 quality % and remainder by Fe and the inevitable slab that consists of of impurity.Then, at 1100 ℃ of lower heating slabs, then under 900 ℃, carry out finish rolling.Under 1100 ℃, it all is the value that is lower than by the value of the above-mentioned temperature T 1 that forms calculating, T2, T3.Carry out in this wise and obtain the hot rolled strip that thickness is 2.3mm.Next, under 1100 ℃, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, in 830 ℃ moistening atmosphere gas, carry out the decarburizing annealing in 100 seconds, thereby obtain the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.023 quality %.Then, coating is with the annealing separation agent of MgO as main component, and the atmosphere of the temperature of the A1 to the table 12 arranges similarly to Example 1, is made as the atmosphere in the table 12 under the switching temperature A1 in table 12 and the A2, under the temperature higher than temperature A2 with nitrogen partial pressure P N2Be made as 0.05, with oxygen gesture Log[P H2O/ P H2] be made as-below 2, be heated to 1200 ℃ with 15 ℃/hour speed, carry out final annealing reaching after 1200 ℃ under hydrogen is 100% atmosphere.
To the sample behind such final annealing, measure situation and the magnetic properties (magneticflux-density B8) of epithelium.At first, about the situation of epithelium, studied the forsterite amount of glass skin membrane and based on the peak position of Mg and the B of GDS.The forsterite amount all is more than 70%.Before GDS measured, making by solid component concentration was that 50% phosphate dihydrogen aluminum solution 100g, solid component concentration are the coating fluid that 20% colloid silica 102g and chromic trioxide 5.4g form.Next, be 5g/m to the steel plate with glass epithelium behind the final annealing by the rear single face of baking 2Mode be coated with coating fluid and dry, then 900 ℃ of lower bakings.The thickness of secondary epithelium in this case is 1.5 μ m.
In addition, magnetic properties (magneticflux-density B8) is measured according to JIS C2556.Further, also tested the epithelium adaptation by following step.At first, making by solid component concentration is that 50% phosphate dihydrogen aluminum solution 100g, solid component concentration are the coating fluid that 20% colloid silica 102g and chromic trioxide 5.4g form.Next, obtaining extra high tension force in order to make the steel plate with glass epithelium behind the final annealing, is 12g/m by single face after the baking 2Mode be coated with coating fluid and dry, then 900 ℃ of lower bakings.This steel plate is wound to the pole of diameter 20 φ, the inboard steel plate that then is determined at curved part exposes the area of peeling off of such epithelium.Peel off area and be 5% when following, be judged as adaptation good.Above test the results are shown in table 12.
Table l2
Figure BDA00003502746800431
As shown in table 12, in the situation that test No.g1, because the 3Log[P in (11) formula under 800 ℃～1100 ℃ H2O/ P H2]+A is lower than top condition, so the decomposition of BN easily carries out, and compares B with top condition near surface enrichment more and ratio tB/tMg diminishes, and epithelium tension force is high especially, and in the situation of such the present embodiment, the epithelium adaptation is bad.In addition, in the situation that test No.g2, because the 3Log[P in (11) formula H2O/ P H2]+A is too high, although therefore the epithelium adaptation is good, does not obtain good magnetic properties.In the situation that test No.g3, because oxygen gesture Log[P H2O/ P H2] too high, so ratio tB/tMg becomes inappropriate value, do not obtain good adaptation.In the situation that test No.g4 and g5, because oxygen gesture Log[P H2O/ P H2] too high, and 3Log[P H2O/ P H2The value of]+A is incorrect, therefore on the basis that does not all obtain good magnetic properties, in the situation that test No.g5 does not also obtain good adaptation.
On the other hand, the switching temperature A1 of test No.g6 that has changed the atmosphere switching temperature is excessively low, does not therefore obtain adaptation and improves effect.In test No.g7, because switching temperature A1 is too high, therefore based on the decomposition of the oxidation of BN in advance, ratio tB/tMg becomes inappropriate value, and magneticflux-density B8 is poor.In test No.g8, because switching temperature A2 is excessively low, so the decomposition of BN in advance, and ratio tB/tMg becomes inappropriate value, and magneticflux-density B8 is also poor.In test No.g9, because switching temperature A2 is too high, so the decomposition of BN delay, ratio tB/tMg is excessive, and magnetic properties is poor.
As by the above as can be known, when the operating condition of final annealing is made as particularly preferred nitrogen partial pressure scope in the present invention, even formed the epithelium that produces special high tensile, also can access the grain-oriented magnetic steel sheet that also has good epithelium adaptation on the good magnetic properties basis having.
＜embodiment 6＞
To study atmospheric condition more than 1100 ℃ as purpose, carried out following test.At first, make and to have the composition that contains Si:3.4 quality %, B:0.0025 quality %, C:0.06 quality %, N:0.008 quality %, S:0.007 quality %, Al:0.03 quality % and remainder by Fe and the inevitable slab that consists of of impurity.Then, at 1100 ℃ of lower heating slabs, then under 900 ℃, carry out finish rolling.Under 1100 ℃, it all is the value that is lower than by the value of the above-mentioned temperature T 1 that forms calculating, T2, T3.Carry out in this wise and obtain the hot rolled strip that thickness is 2.3mm.Next, under 1100 ℃, hot rolled strip is annealed.Then, carry out the cold rolling cold-rolled steel strip that thickness is 0.22mm that obtains.Then, in 830 ℃ moistening atmosphere gas, carry out the decarburizing annealing in 100 seconds, thereby obtain the decarburizing annealing steel band.Next, in containing the atmosphere of ammonia, the decarburizing annealing steel band is annealed, thereby make the nitrogen in the steel band increase to 0.023 quality %.Then, be coated with the annealing separation agent of MgO as main component the nitrogen partial pressure P of near 800 ℃ atmosphere N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-0.5, with the nitrogen partial pressure P under 800 ℃～1100 ℃ N2Be made as 0.5, with oxygen gesture Log[P H2O/ P H2] be made as-1, in the lower atmosphere that is made as in the table 13 more than 1100 ℃, be heated to 1200 ℃ with 15 ℃/hour speed, carry out final annealing reaching after 1200 ℃ under hydrogen is 100% atmosphere.
To the sample behind such final annealing, measure situation and the magnetic properties (magneticflux-density B8) of epithelium.At first, the situation of epithelium has been studied the forsterite amount of glass skin membrane and the Mg that is obtained by GDS and the peak position of B.The forsterite amount all is more than 70%.Before GDS measured, making by solid component concentration was that 50% phosphate dihydrogen aluminum solution 100g, solid component concentration are the coating fluid that 20% colloid silica 102g and chromic trioxide 5.4g form.Next, be 5g/m to the steel plate with glass epithelium behind the final annealing by the rear single face of baking 2Mode be coated with coating fluid and dry, then 900 ℃ of lower bakings.The thickness of secondary epithelium in this case is 1.5 μ m.
In addition, magnetic properties (magneticflux-density B8) is measured according to JIS C2556.Further, also tested the epithelium adaptation by following step.At first, making by solid component concentration is that 50% phosphate dihydrogen aluminum solution 100g, solid component concentration are the coating fluid that 20% colloid silica 102g and chromic trioxide 5.4g form.Next, in order to give extra high tension force to the steel plate with glass epithelium behind the final annealing, be 12g/m by single face after the baking 2Mode be coated with coating fluid and dry, then 900 ℃ of lower bakings.This steel plate is wound to the pole of diameter 20 φ, the inboard steel plate that then is determined at curved part exposes the area of peeling off of such epithelium.Peel off area and be 5% when following, be judged as adaptation good.Above test the results are shown in table 13.
Table l3
Figure BDA00003502746800451
As shown in table 13, in the situation that test No.h1, because the nitrogen partial pressure P more than 1100 ℃ N2And oxygen gesture Log[P H2O/ P H2] too high, therefore not carrying out the decomposition of BN, ratio tB/tMg is excessive and magnetic properties is poor.In addition, in the situation that test No.h2, because oxygen gesture Log[P H2O/ P H2] too high, so ratio tB/tMg is excessive and magnetic properties is poor.In the situation that test No.h3, because nitrogen partial pressure P N2Too high, so ratio tB/tMg is too small and in the situation of the epithelium that has formed the special high tensile of generation as the present embodiment, do not have the effect of improving of epithelium adaptation.
As by the above as can be known, when final annealing is made as operating condition of the present invention, even in the situation that given extra high tension force, also can access the grain-oriented magnetic steel sheet that on the basis with good magnetic properties, also has good epithelium adaptation.
Utilizability on the industry
The present invention for example can be used in the electro-magnetic steel plate manufacturing industry and electro-magnetic steel plate utilizes in the industry.

Claims (5)

1. grain-oriented magnetic steel sheet, it contains the Mn of Si, the 0.05 quality %～1 quality % of 0.8 quality %～7 quality %, the B of 0.0005 quality %～0.0080 quality %, the content of Al, C, N, S and Se is respectively below the 0.005 quality %, remainder is made of Fe and inevitable impurity, has the glass epithelium that forms as the composite oxides of main body by with forsterite at surface of steel plate, it is characterized in that
Formed thickness on the surface of described glass epithelium and be more than the 1 μ m and when under the condition of the secondary epithelium below the 2 μ m surface of described secondary epithelium being carried out the grow discharge optical emission spectrometry analysis and be GDS, peak with luminous intensity of the peak position of the luminous intensity B different from the peak position of the luminous intensity of Mg, the peak position of the luminous intensity of the B of the described surface of steel plate of distance is darker than the peak position of the luminous intensity of the Mg of the described surface of steel plate of distance, wherein, described secondary epithelium contains in chromic trioxide and the chromic salt a kind or 2 kinds of being selected from of the colloidal silicon-dioxide of 26～38 quality % and 4～12 quality %, remainder is made of aluminium dihydrogen phosphate
And be among the peak of luminous intensity of the described B that observes of GDS by the grow discharge optical emission spectrometry analysis, apart from described surface of steel plate farthest person's peak generation time tB with following formula (1) expression,
tMg×1.6≤tB≤tMg×5?（1）
Herein, tMg represents the peak generation time of Mg.
2. the manufacture method of a grain-oriented magnetic steel sheet is characterized in that, it has following operation:
Heating process, in this operation, the electro-magnetic steel plate starting material are heated under the temperature of regulation, described electro-magnetic steel plate starting material contain Si, the 0.01 quality % of 0.8 quality %～7 quality %～acid-solubility Al of 0.0065 quality %, the Mn of the N of 0.004 quality %～0.012 quality %, 0.05 quality %～1 quality %, the B of 0.0005 quality %～0.0080 quality %, and among S and the Se at least a kind of being selected from that contains 0.003 quality %～0.015 quality % by total amount, C content is below the 0.085 quality %, and remainder is made of Fe and inevitable impurity;
Obtain the operation of hot rolled strip, in this operation, warmed-up described silicon steel starting material are carried out hot rolling obtain hot rolled strip;
Obtain the annealing operation of steel band in this operation, anneals to obtain the steel band of annealing to described hot rolled strip;
Obtain the operation of cold-rolled steel strip, in this operation, described annealed steel band is carried out the cold rolling cold-rolled steel strip that obtains more than 1 time;
Obtain the operation of decarburizing annealing steel band, in this operation, described cold-rolled steel strip is carried out decarburizing annealing, thereby obtained occuring the decarburizing annealing steel band of primary recrystallization;
Painting process in this operation, will be coated described decarburizing annealing steel band as the annealing separation agent of main component with MgO; With
The operation of secondary recrystallization occurs, and in this operation, the final annealing by described decarburizing annealing steel band makes it that secondary recrystallization occur,
And the manufacture method of described grain-oriented magnetic steel sheet also has following operation: from begin described decarburizing annealing manifest to the final annealing secondary recrystallization during, the nitriding treatment that the N content of described decarburizing annealing steel band is increased,
When containing S and Se in the described silicon steel starting material, the temperature of described regulation is temperature T 1(℃ shown in the following formula (2)) temperature T 2(℃ shown in following, the following formula (3)) temperature T 3(℃ shown in the following and following formula (4)) below;
When not containing Se in the described silicon steel starting material, the temperature of described regulation is temperature T 1(℃ shown in the following formula (2)) temperature T 3(℃ shown in the following and following formula (4)) below;
When not containing S in the described silicon steel starting material, the temperature of described regulation is temperature T 2(℃ shown in the following formula (3)) temperature T 3(℃ shown in the following and following formula (4)) below, the finish rolling end temp Tf of described hot rolling satisfies following formula (5),
The amount of BN in the described hot rolled strip, MnS and MnSe satisfies following formula (6), (7) and (8), and the temperature during final annealing is 800 ℃～1100 ℃ temperature range, and atmosphere satisfies following formula (9) and (10),
T1=14855/(6.82-log([Mn]×[S]))-273?（2）
T2=10733/(4.08-log([Mn]×[Se]))-273?（3）
T3=16000/(5.92-log([B]×[N]))-273?（4）
Tf≤1000-10000×[B]?（5）
B asBN≥0.0005?（6）
[B]-B asBN≤0.001?（7）
S asMnS+0.5×Se asMnSe≥0.002?（8）
0.75≥P N2≥0.2?（9）
-0.7≥Log[P H2O/P H2]?（10）
Herein, [Mn] represents the raw-material Mn content of described silicon steel (quality %), [S] represents the raw-material S content of described silicon steel (quality %), [Se] represents the raw-material Se content of described silicon steel (quality %), [B] represents the raw-material B content of described silicon steel (quality %), [N] represents the raw-material N content of described silicon steel (quality %), B AsBNBe illustrated in the amount (quality %) of the B that separates out as BN in the described hot rolled strip, S AsMnSBe illustrated in the amount (quality %) of the S that separates out as MnS in the described hot rolled strip, Se AsMnSeBe illustrated in the amount (quality %) of the Se that separates out as MnSe in the described hot rolled strip, and P N2The expression nitrogen partial pressure, P H2O, P H2Represent respectively steam partial pressure, hydrogen dividing potential drop.
3. the manufacture method of grain-oriented magnetic steel sheet according to claim 2 is characterized in that, the temperature during final annealing is 800 ℃～1100 ℃ temperature range, and atmosphere satisfies following formula (11),
4Log[P N2]=3Log[P H2O/P H2]+A+3455/T?（11）
Herein ,-3.72 〉=3Log[P H2O/ P H2]+A 〉=-5.32 and-0.7 〉=Log[P H2O/ P H2], A is for pressing based on Log[P H2O/ P H2] make 3Log[P H2O/ P H2]+A enters the definite constant of mode of the scope of regulation, and T represents absolute temperature.
4. the manufacture method of grain-oriented magnetic steel sheet according to claim 2 is characterized in that, the atmosphere when final annealing more than 1100 ℃ satisfies following formula (12) and (13),
0.1≥P N2?（12）
-2≥Log[P H2O/P H2]?（13）。
5. the manufacture method of grain-oriented magnetic steel sheet according to claim 2, it is characterized in that, described electro-magnetic steel plate starting material further contain be selected from that Cr:0.3 quality % is following, Cu:0.4 quality % following, Ni:1 quality % is following, P:0.5 quality % is following, Mo:0.1 quality % is following, Sn:0.3 quality % is following, Sb:0.3 quality % is following and Bi:0.01 quality % with lower at least a kind.
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